Ring opening cross-metathesis reaction of cyclic olefins with seed oils and the like

ABSTRACT

This invention relates generally to olefin metathesis, and more particularly relates to the ring-opening, ring insertion cross-metathesis of cyclic olefins with internal olefins such as seed oils and the like. In one embodiment, a method is provided for carrying out a catalytic ring-opening cross-metathesis reaction, comprising contacting at least one olefinic substrate with at least one cyclic olefin as a cross metathesis partner, in the presence of a ruthenium alkylidene olefin metathesis catalyst under conditions effective to allow ring insertion cross metathesis whereby the cyclic olefin is simultaneously opened and inserted into the olefinic substrate. The invention has utility in the fields of catalysis, organic synthesis, and industrial chemistry.

RELATED APPLICATIONS

This application claims priority to U.S. Provisional Application Ser.No. 60/853,300, filed Jul. 12, 2006, the disclosure of which isincorporated herein by reference.

TECHNICAL FIELD

This invention relates generally to olefin metathesis, and moreparticularly relates to the ring-opening, ring insertioncross-metathesis of cyclic olefins with internal olefins such as seedoils and the like. The invention has utility in the fields of catalysis,organic synthesis, and industrial chemistry.

BACKGROUND

In the past 15 years, ruthenium olefin metathesis catalysts have firmlyestablished olefin metathesis as a versatile and reliable synthetictechnique for organic syntheses. The exceptionally wide scope ofsubstrates and functional group tolerance makes olefin metathesis avaluable technique. In this application, the use of olefin crossmetathesis to produce alpha-olefins is another example of the usefulnessand the robustness of olefin metathesis technology. Compared totraditional synthetic organic techniques, olefin metathesis efficientlyproduces compounds that are otherwise hard to synthesize. Numerous manhours of research have resulted in the elucidation of many olefinmetathesis reactions catalyzed by various transition metal complexes. Inparticular, certain ruthenium and osmium carbene compounds, known as“Grubbs' catalysts,” have been identified as effective catalysts forolefin metathesis reactions such as, for example, cross-metathesis (CM),ring-closing metathesis (RCM), ring-opening metathesis (ROM), ringopening cross metathesis (ROCM), ring-opening metathesis polymerization(ROMP) or acyclic diene metathesis (ADMET) polymerization.

ROCM is a version of cross metathesis and historically has beenunderutilized mainly due the difficulty of controlling selectively. ROCMis an intermolecular exchange of a cyclic olefin and an acyclic olefin.In these instances, release of ring strain is the driving force for thereaction to proceed. A review of ROCM is provided by Schrader andSnapper in Handbook of Metathesis, Volume 2: Applications in OrganicSynthesis (R. H. Grubbs Ed.), Wiley-VCH Verlag GmbH & Co. KGaA,Weinheim, 2003, pp 205-237.

Early ROCM examples were low yielding reactions with poor selectivities.Even with these shortcomings, ROCM has become an important fixture inmetathesis history because ROCM was the key reaction used by YvesChauvin to propose the currently accepted metathesis mechanism thatbears his name, i.e. the Chauvin mechanism. Chauvin proposed theinterchange of metal carbenes via a metallocyclobutane ring as analternative mechanism to the then-accepted pair-wise mechanism forolefin cross metathesis. The metallocyclobutane mechanism was proposedbased on the ROCM of cyclopentene with 2-pentene, shown in Scheme 1,which resulted in a statistical product distribution (1:2:1 of compounds1, 2, and 3 respectively). In the pair-wise mechanism only compound 2would be expected to form, at low conversions. Chauvin was rewarded forhis insight and contributions to metathesis by sharing the 2005 NobelPrize in Chemistry with Dr. Robert Grubbs and Dr. Richard Schrock.

ROCM reactions using cyclododecene and methyl oleate or oleyl acetatehave been reported. The reactions employed an ill-defined tungstencatalyst system to produce the ring inserted product, as shown in Scheme2.

There is an ongoing need in the art for methods and systems that wouldallow ring insertion cross metathesis of cyclic olefins into internalolefins, e.g., seed oils and the like. This type of reaction would beuseful in the preparation of various useful products, including, by wayof example, chain-extended trialkylglycerides (TAGs) and chain-extendedfatty acid methyl esters (FAMEs). An ideal such reaction could beimplemented in the preparation of metathesis products useful as bindersin urethane foams, latex pains, printing inks, and high melting pointwaxes.

SUMMARY OF THE DISCLOSURE

Accordingly, the invention is directed to addressing one or more of theaforementioned issues, and, in one embodiment, provides a method forcarrying out a catalytic ring-opening cross-metathesis reaction. Themethod comprises contacting at least one olefinic substrate with atleast one cyclic olefin as a cross metathesis partner, in the presenceof a ruthenium alkylidene olefin metathesis catalyst. The at least oneolefinic substrate is selected from: (i) an unsaturated fatty acid; (ii)an unsaturated fatty alcohol; (iii) an esterification product of anunsaturated fatty acid with an alcohol; and (iv) an esterificationproduct of a saturated fatty acid with an unsaturated alcohol. Thecontacting is carried out under conditions effective to allow ringinsertion cross metathesis whereby the cyclic olefin is simultaneouslyopened and inserted into the olefinic substrate.

In another embodiment, the invention provides a method for manufacturinga wax. The method comprises contacting at least one olefinic substratewith at least one cyclic olefin as a cross metathesis partner in thepresence of a ruthenium alkylidene olefin metathesis catalyst. The atleast one olefinic substrate is selected from: (i) an unsaturated fattyacid or derivative thereof; (ii) an unsaturated fatty alcohol orderivative thereof; (iii) an esterification product of an unsaturatedfatty acid with an alcohol; and (iv) an esterification product of asaturated fatty acid with an unsaturated alcohol. The reaction iscarried out under conditions effective to allow ring insertion crossmetathesis whereby the cyclic olefin is simultaneously opened andinserted into the olefinic substrate to provide an olefinic product. Themethod further comprises optionally hydrogenating the olefinic product,wherein the hydrogenation may be partial or complete hydrogenation.

In a still further embodiment, the invention provides a method forcarrying out a catalytic ring-opening cross-metathesis reaction. Themethod comprises contacting at least one olefinic substrate with atleast one cyclic olefin functionalized with a functional group as across metathesis partner, in the presence of a ruthenium alkylideneolefin metathesis catalyst. The at least one olefinic substrate isselected from: (i) an unsaturated fatty acid; (ii) an unsaturated fattyalcohol; (iii) an esterification product of an unsaturated fatty acidwith an alcohol; and (iv) an esterification product of a saturated fattyacid with an unsaturated alcohol. The contacting is carried out underconditions effective to allow ring insertion cross metathesis wherebythe cyclic olefin is simultaneously opened and inserted into theolefinic substrate.

In a still further embodiment, the invention provides a method forcarrying our a catalytic ring-opening cross metathesis reaction. Themethod comprises contacting at least one olefinic substrate with atleast one cyclic olefin as a cross metathesis partner, in the presenceof a ruthenium alkylidene olefin metathesis catalyst. The catalyst ispresent in an amount that is less than 1000 ppm relative to the olefinicsubstrate, and the at least one olefinic substrate is selected from (i)an unsaturated fatty acid, (ii) an unsaturated fatty alcohol, (iii) anesterification product of an unsaturated fatty acid with an alcohol, and(iv) an esterification product of a saturated fatty acid with anunsaturated alcohol.

In a further embodiment, the invention provides a reaction system forcarrying out a catalytic ring-opening cross-metathesis reactioncomprising at least one olefinic substrate, at least one cyclic olefin,and a ruthenium alkylidene olefin metathesis catalyst. The at least oneolefinic substrate is selected from (i) an unsaturated fatty acid, (ii)an unsaturated fatty alcohol, (iii) an esterification product of anunsaturated fatty acid with an alcohol, and (iv) an esterificationproduct of a saturated fatty acid with an unsaturated alcohol.

In a still further embodiment, the invention provides a reaction systemfor manufacturing a wax. The reaction system comprises at least oneolefinic substrate, at least one cyclic olefin, and a rutheniumalkylidene olefin metathesis catalyst. The at least one olefinicsubstrate is selected from: (i) an unsaturated fatty acid; (ii) anunsaturated fatty alcohol; (iii) an esterification product of anunsaturated fatty acid with an alcohol; and (iv) an esterificationproduct of a saturated fatty acid with an unsaturated alcohol.

In a still further embodiment, the invention provides a ring-openingcross-metathesis product prepared using any of the methods and reactionsystems disclosed herein.

In a still further embodiment, the invention provides a chain-extendedolefinic substrate formed by a catalytic ring-opening cross-metathesisreaction. The reaction comprises contacting: (a) at least one olefinicsubstrate selected from (i) an unsaturated fatty acid, (ii) anunsaturated fatty alcohol, (iii) an esterification product of anunsaturated fatty acid with an alcohol, and (iv) an esterificationproduct of a saturated fatty acid with an unsaturated alcohol, with (b)at least one cyclic olefin as a cross metathesis partner, in thepresence of (c) a ruthenium alkylidene olefin metathesis catalyst, underconditions effective to allow ring insertion cross metathesis wherebythe cyclic olefin is simultaneously opened and inserted into theolefinic substrate to form the chain-extended olefinic substrate.

In a still further embodiment, the invention provides a kit of parts forcarrying out a catalytic ring-opening cross metathesis reaction. The kitof parts comprises at least one olefinic substrate and a rutheniumalkylidene olefin metathesis catalyst. The at least one olefinicsubstrate is selected from (i) an unsaturated fatty acid, (ii) anunsaturated fatty alcohol, (iii) an esterification product of anunsaturated fatty acid with an alcohol, and (iv) an esterificationproduct of a saturated fatty acid with an unsaturated alcohol. The kitof parts further comprises: (a) at least one cyclic olefin; or (b)instructions for adding a cyclic olefin to the at least one olefinicsubstrate.

In a still further embodiment, the invention provides a kit of parts formanufacturing a wax. The kit of parts comprises at least one olefinicsubstrate and a ruthenium alkylidene olefin metathesis catalyst. The atleast one olefinic substrate is selected from (i) an unsaturated fattyacid, (ii) an unsaturated fatty alcohol, (iii) an esterification productof an unsaturated fatty acid with an alcohol, and (iv) an esterificationproduct of a saturated fatty acid with an unsaturated alcohol. The kitof parts further comprises: (a) at least one cyclic olefin; or (b)instructions for adding a cyclic olefin to the at least one olefinicsubstrate. The kit of parts further comprises instructions forhydrogenating metathesis products.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a typical GC-MS chromatogram of ROCM (n=1) products.

FIG. 2 is a MALDI-TOF spectrum of ROCM Product (n=1) from metathesis of9C18 and COE

DETAILED DESCRIPTION OF THE DISCLOSURE Terminology and Definitions

Unless otherwise indicated, the invention is not limited to specificreactants, substituents, catalysts, reaction conditions, or the like, assuch may vary. It is also to be understood that the terminology usedherein is for the purpose of describing particular embodiments only andis not intended to be limiting.

As used in the specification and the appended claims, the singular forms“a,” “an,” and “the” include plural referents unless the context clearlydictates otherwise. Thus, for example, reference to “an α-olefin”includes a single α-olefin as well as a combination or mixture of two ormore α-olefin, reference to “a substituent” encompasses a singlesubstituent as well as two or more substituents, and the like.

As used in the specification and the appended claims, the terms “forexample,” “for instance,” “such as,” or “including” are meant tointroduce examples that further clarify more general subject matter.Unless otherwise specified, these examples are provided only as an aidfor understanding the invention, and are not meant to be limiting in anyfashion.

In this specification and in the claims that follow, reference will bemade to a number of terms, which shall be defined to have the followingmeanings:

The term “alkyl” as used herein refers to a linear, branched, or cyclicsaturated hydrocarbon group typically although not necessarilycontaining 1 to about 24 carbon atoms, preferably 1 to about 12 carbonatoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl,t-butyl, octyl, decyl, and the like, as well as cycloalkyl groups suchas cyclopentyl, cyclohexyl and the like. Generally, although again notnecessarily, alkyl groups herein contain 1 to about 12 carbon atoms. Theterm “lower alkyl” intends an alkyl group of 1 to 6 carbon atoms, andthe specific term “cycloalkyl” intends a cyclic alkyl group, typicallyhaving 4 to 8, preferably 5 to 7, carbon atoms. The term “substitutedalkyl” refers to alkyl substituted with one or more substituent groups,and the terms “heteroatom-containing alkyl” and “heteroalkyl” refer toalkyl in which at least one carbon atom is replaced with a heteroatom.If not otherwise indicated, the terms “alkyl” and “lower alkyl” includelinear, branched, cyclic, unsubstituted, substituted, and/orheteroatom-containing alkyl and lower alkyl, respectively.

The term “alkylene” as used herein refers to a difunctional linear,branched, or cyclic alkyl group, where “alkyl” is as defined above.

The term “alkenyl” as used herein refers to a linear, branched, orcyclic hydrocarbon group of 2 to about 24 carbon atoms containing atleast one double bond, such as ethenyl, n-propenyl, isopropenyl,n-butenyl, isobutenyl, octenyl, decenyl, tetradecenyl, hexadecenyl,eicosenyl, tetracosenyl, and the like. Preferred alkenyl groups hereincontain 2 to about 12 carbon atoms. The term “lower alkenyl” intends analkenyl group of 2 to 6 carbon atoms, and the specific term“cycloalkenyl” intends a cyclic alkenyl group, preferably having 5 to 8carbon atoms. The term “substituted alkenyl” refers to alkenylsubstituted with one or more substituent groups, and the terms“heteroatom-containing alkenyl” and “heteroalkenyl” refer to alkenyl inwhich at least one carbon atom is replaced with a heteroatom. If nototherwise indicated, the terms “alkenyl” and “lower alkenyl” includelinear, branched, cyclic, unsubstituted, substituted, and/orheteroatom-containing alkenyl and lower alkenyl, respectively.

The term “alkenylene” as used herein refers to a difunctional linear,branched, or cyclic alkenyl group, where “alkenyl” is as defined above.

The term “alkynyl” as used herein refers to a linear or branchedhydrocarbon group of 2 to about 24 carbon atoms containing at least onetriple bond, such as ethynyl, n-propynyl, and the like. Preferredalkynyl groups herein contain 2 to about 12 carbon atoms. The term“lower alkynyl” intends an alkynyl group of 2 to 6 carbon atoms. Theterm “substituted alkynyl” refers to alkynyl substituted with one ormore substituent groups, and the terms “heteroatom-containing alkynyl”and “heteroalkynyl” refer to alkynyl in which at least one carbon atomis replaced with a heteroatom. If not otherwise indicated, the terms“alkynyl” and “lower alkynyl” include linear, branched, unsubstituted,substituted, and/or heteroatom-containing alkynyl and lower alkynyl,respectively.

The term “alkoxy” as used herein intends an alkyl group bound through asingle, terminal ether linkage; that is, an “alkoxy” group may berepresented as —O-alkyl where alkyl is as defined above. A “loweralkoxy” group intends an alkoxy group containing 1 to 6 carbon atoms.Analogously, “alkenyloxy” and “lower alkenyloxy” respectively refer toan alkenyl and lower alkenyl group bound through a single, terminalether linkage, and “alkynyloxy” and “lower alkynyloxy” respectivelyrefer to an alkynyl and lower alkynyl group bound through a single,terminal ether linkage.

The term “aryl” as used herein, and unless otherwise specified, refersto an aromatic substituent containing a single aromatic ring or multiplearomatic rings that are fused together, directly linked, or indirectlylinked (such that the different aromatic rings are bound to a commongroup such as a methylene or ethylene moiety). Preferred aryl groupscontain 5 to 24 carbon atoms, and particularly preferred aryl groupscontain 5 to 14 carbon atoms. Exemplary aryl groups contain one aromaticring or two fused or linked aromatic rings, e.g., phenyl, naphthyl,biphenyl, diphenylether, diphenylamine, benzophenone, and the like.“Substituted aryl” refers to an aryl moiety substituted with one or moresubstituent groups, and the terms “heteroatom-containing aryl” and“heteroaryl” refer to aryl substituents in which at least one carbonatom is replaced with a heteroatom, as will be described in furtherdetail infra.

The term “aryloxy” as used herein refers to an aryl group bound througha single, terminal ether linkage, wherein “aryl” is as defined above. An“aryloxy” group may be represented as —O-aryl where aryl is as definedabove. Preferred aryloxy groups contain 5 to 24 carbon atoms, andparticularly preferred aryloxy groups contain 5 to 14 carbon atoms.Examples of aryloxy groups include, without limitation, phenoxy,o-halo-phenoxy, m-halo-phenoxy, p-halo-phenoxy, o-methoxy-phenoxy,m-methoxy-phenoxy, p-methoxy-phenoxy, 2,4-dimethoxy-phenoxy,3,4,5-trimethoxy-phenoxy, and the like.

The term “alkaryl” refers to an aryl group with an alkyl substituent,and the term “aralkyl” refers to an alkyl group with an arylsubstituent, wherein “aryl” and “alkyl” are as defined above. Preferredalkaryl and aralkyl groups contain 6 to 24 carbon atoms, andparticularly preferred alkaryl and aralkyl groups contain 6 to 16 carbonatoms. Alkaryl groups include, for example, p-methylphenyl,2,4-dimethylphenyl, p-cyclohexylphenyl, 2,7-dimethylnaphthyl,7-cyclooctylnaphthyl, 3-ethyl-cyclopenta-1,4-diene, and the like.Examples of aralkyl groups include, without limitation, benzyl,2-phenyl-ethyl, 3-phenyl-propyl, 4-phenyl-butyl, 5-phenyl-pentyl,4-phenylcyclohexyl, 4-benzylcyclohexyl, 4-phenylcyclohexylmethyl,4-benzylcyclohexylmethyl, and the like. The terms “alkaryloxy” and“aralkyloxy” refer to substituents of the formula —OR wherein R isalkaryl or aralkyl, respectively, as just defined.

The term “acyl” refers to substituents having the formula —(CO)-alkyl,—(CO)-aryl, or —(CO)-aralkyl, and the term “acyloxy” refers tosubstituents having the formula —O(CO)-alkyl, —O(CO)-aryl, or—O(CO)-aralkyl, wherein “alkyl,” “aryl, and “aralkyl” are as definedabove.

The terms “cyclic” and “ring” refer to alicyclic or aromatic groups thatmay or may not be substituted and/or heteroatom containing, and that maybe monocyclic, bicyclic, or polycyclic. The term “alicyclic” is used inthe conventional sense to refer to an aliphatic cyclic moiety, asopposed to an aromatic cyclic moiety, and may be monocyclic, bicyclic,or polycyclic.

The terms “halo” and “halogen” are used in the conventional sense torefer to a chloro, bromo, fluoro, or iodo substituent.

“Hydrocarbyl” refers to univalent hydrocarbyl radicals containing 1 toabout 30 carbon atoms, preferably 1 to about 24 carbon atoms, mostpreferably 1 to about 12 carbon atoms, including linear, branched,cyclic, saturated, and unsaturated species, such as alkyl groups,alkenyl groups, aryl groups, and the like. The term “lower hydrocarbyl”intends a hydrocarbyl group of 1 to 6 carbon atoms, preferably 1 to 4carbon atoms, and the term “hydrocarbylene” intends a divalenthydrocarbyl moiety containing 1 to about 30 carbon atoms, preferably 1to about 24 carbon atoms, most preferably 1 to about 12 carbon atoms,including linear, branched, cyclic, saturated and unsaturated species.The term “lower hydrocarbylene” intends a hydrocarbylene group of 1 to 6carbon atoms. “Substituted hydrocarbyl” refers to hydrocarbylsubstituted with one or more substituent groups, and the terms“heteroatom-containing hydrocarbyl” and “heterohydrocarbyl” refer tohydrocarbyl in which at least one carbon atom is replaced with aheteroatom. Similarly, “substituted hydrocarbylene” refers tohydrocarbylene substituted with one or more substituent groups, and theterms “heteroatom-containing hydrocarbylene” and “heterohydrocarbylene”refer to hydrocarbylene in which at least one carbon atom is replacedwith a heteroatom. Unless otherwise indicated, the term “hydrocarbyl”and “hydrocarbylene” are to be interpreted as including substitutedand/or heteroatom-containing hydrocarbyl and hydrocarbylene moieties,respectively.

The term “heteroatom-containing” as in a “heteroatom-containinghydrocarbyl group” refers to a hydrocarbon molecule or a hydrocarbylmolecular fragment in which one or more carbon atoms is replaced with anatom other than carbon, e.g., nitrogen, oxygen, sulfur, phosphorus orsilicon, typically nitrogen, oxygen or sulfur. Similarly, the term“heteroalkyl” refers to an alkyl substituent that isheteroatom-containing, the term “heterocyclic” refers to a cyclicsubstituent that is heteroatom-containing, the terms “heteroaryl” andheteroaromatic” respectively refer to “aryl” and “aromatic” substituentsthat are heteroatom-containing, and the like. It should be noted that a“heterocyclic” group or compound may or may not be aromatic, and furtherthat “heterocycles” may be monocyclic, bicyclic, or polycyclic asdescribed above with respect to the term “aryl.” Examples of heteroalkylgroups include alkoxyaryl, alkylsulfanyl-substituted alkyl, N-alkylatedamino alkyl, and the like. Examples of heteroaryl substituents includepyrrolyl, pyrrolidinyl, pyridinyl, quinolinyl, indolyl, pyrimidinyl,imidazolyl, 1,2,4-triazolyl, tetrazolyl, etc., and examples ofheteroatom-containing alicyclic groups are pyrrolidino, morpholino,piperazino, piperidino, etc.

By “substituted” as in “substituted hydrocarbyl,” “substituted alkyl,”“substituted aryl,” and the like, as alluded to in some of theaforementioned definitions, is meant that in the hydrocarbyl, alkyl,aryl, or other moiety, at least one hydrogen atom bound to a carbon (orother) atom is replaced with one or more non-hydrogen substituents.Examples of such substituents include, without limitation: functionalgroups referred to herein as “Fn,” such as halo, hydroxyl, sulfhydryl,C₁-C₂₄ alkoxy, C₂-C₂₄ alkenyloxy, C₂-C₂₄ alkynyloxy, C₅-C₂₄ aryloxy,C₆-C₂₄ aralkyloxy, C₆-C₂₄ alkaryloxy, acyl (including C₂-C₂₄alkylcarbonyl (—CO-alkyl) and C₆-C₂₄ arylcarbonyl (—CO-aryl)), acyloxy(—O-acyl, including C₂-C₂₄ alkylcarbonyloxy (—O—CO-alkyl) and C₆-C₂₄arylcarbonyloxy (—O—CO-aryl)), C₂-C₂₄ alkoxycarbonyl (—(CO)—O-alkyl),C₆-C₂₄ aryloxycarbonyl (—(CO)—O-aryl), halocarbonyl (—CO)—X where X ishalo), C₂-C₂₄ alkylcarbonato (—O—(CO)—O-alkyl), C₆-C₂₄ arylcarbonato(—O—(CO)—O-aryl), carboxy (—COOH), carboxylato (—COO⁻), carbamoyl(—(CO)—NH₂), mono-(C₁-C₂₄ alkyl)-substituted carbamoyl (—(CO)—NH(C₁-C₂₄alkyl)), di-(C₁-C₂₄ alkyl)-substituted carbamoyl (—(CO)—N(C₁-C₂₄alkyl)₂), mono-(C₅-C₂₄ aryl)-substituted carbamoyl (—(CO)—NH-aryl),di-(C₅-C₂₄ aryl)-substituted carbamoyl (—(CO)—N(C₅-C₂₄ aryl)₂),di-N—(C₁-C₂₄ alkyl), N—(C₅-C₂₄ aryl)-substituted carbamoyl,thiocarbamoyl (—(CS)—NH₂), mono-(C₁-C₂₄ alkyl)-substituted thiocarbamoyl(—(CO)—NH(C₁-C₂₄ alkyl)), di-(C₁-C₂₄ alkyl)-substituted thiocarbamoyl(—(CO)—N(C₁-C₂₄ alkyl)₂), mono-(C₅-C₂₄ aryl)-substituted thiocarbamoyl(—(CO)—NH-aryl), di-(C₅-C₂₄ aryl)-substituted thiocarbamoyl(—(CO)—N(C₅-C₂₄ aryl)₂), di-N—(C₁-C₂₄ alkyl), N—(C₅-C₂₄aryl)-substituted thiocarbamoyl, carbamido (—NH—(CO)—NH₂), cyano(—C≡N),cyanato (—O—C≡N), thiocyanato (—S—C≡N), formyl (—(CO)—H), thioformyl(—(CS)—H), amino (—NH₂), mono-(C₁-C₂₄ alkyl)-substituted amino,di-(C₁-C₂₄ alkyl)-substituted amino, mono-(C₅-C₂₄ aryl)-substitutedamino, di-(C₅-C₂₄ aryl)-substituted amino, C₂-C₂₄ alkylamido(—NH—(CO)-alkyl), C₆-C₂₄ arylamido (—NH—(CO)-aryl), imino (—CR═NH whereR=hydrogen, C₁-C₂₄ alkyl, C₅-C₂₄ aryl, C₆-C₂₄ alkaryl, C₆-C₂₄ aralkyl,etc.), C₂-C₂₀ alkylimino (—CR═N(alkyl), where R=hydrogen, C₁-C₂₄ alkyl,C₅-C₂₄ aryl, C₆-C₂₄ alkaryl, C₆-C₂₄ aralkyl, etc.), arylimino(—CR═N(aryl), where R=hydrogen, C₁-C₂₀ alkyl, C₅-C₂₄ aryl, C₆-C₂₄alkaryl, C₆-C₂₄ aralkyl, etc.), nitro (—NO₂), nitroso (—NO), sulfo(—SO₂—OH), sulfonato (—SO₂—O⁻), C₁-C₂₄ alkylsulfanyl (—S-alkyl; alsotermed “alkylthio”), C₅-C₂₄ arylsulfanyl (—S-aryl; also termed“arylthio”), C₁-C₂₄ alkylsulfinyl (—(SO)-alkyl), C₅-C₂₄ arylsulfinyl(—(SO)-aryl), C₁-C₂₄ alkylsulfonyl (—SO₂-alkyl), C₅-C₂₄ arylsulfonyl(—SO₂-aryl), boryl (—BH₂), borono (—B(OH)₂), boronato (—B(OR)₂ where Ris alkyl or other hydrocarbyl), phosphono (—P(O)(OH)₂), phosphonato(—P(O)(O⁻)₂), phosphinato (—P(O)(O⁻)), phospho (—PO₂), and phosphino(—PH₂); and the hydrocarbyl moieties C₁-C₂₄ alkyl (preferably C₁-C₁₂alkyl, more preferably C₁-C₆ alkyl), C₂-C₂₄ alkenyl (preferably C₂-C₁₂alkenyl, more preferably C₂-C₆ alkenyl), C₂-C₂₄ alkynyl (preferablyC₂-C₁₂ alkynyl, more preferably C₂-C₆ alkynyl), C₅-C₂₄ aryl (preferablyC₅-C₁₄ aryl), C₆-C₂₄ alkaryl (preferably C₆-C₁₆ alkaryl), and C₆-C₂₄aralkyl (preferably C₆-C₁₆ aralkyl).

By “functionalized” as in “functionalized hydrocarbyl,” “functionalizedalkyl,” “functionalized olefin,” “functionalized cyclic olefin,” and thelike, is meant that in the hydrocarbyl, alkyl, olefin, cyclic olefin, orother moiety, at least one hydrogen atom bound to a carbon (or other)atom is replaced with one or more functional groups such as thosedescribed hereinabove.

In addition, the aforementioned functional groups may, if a particulargroup permits, be further substituted with one or more additionalfunctional groups or with one or more hydrocarbyl moieties such as thosespecifically enumerated above. Analogously, the above-mentionedhydrocarbyl moieties may be further substituted with one or morefunctional groups or additional hydrocarbyl moieties such as thosespecifically enumerated.

“Optional” or “optionally” means that the subsequently describedcircumstance may or may not occur, so that the description includesinstances where the circumstance occurs and instances where it does not.For example, the phrase “optionally substituted” means that anon-hydrogen substituent may or may not be present on a given atom, and,thus, the description includes structures wherein a non-hydrogensubstituent is present and structures wherein a non-hydrogen substituentis not present.

A “kit of parts,” as used herein, refers to a packaged collection ofrelated components. Unless otherwise specified, the components of a kitof parts may be packaged individually or together in any combination.

A “reaction system,” as used herein, refers to a functionally relatedgroup of components.

Methods and Compositions of the Disclosure I. First EmbodimentRing-Opening, Ring Insertion Cross-Metathesis Method of a Cyclic Olefinand an Internal Olefin as an Olefinic Substrate

In a first embodiment, the invention provides an olefin cross-metathesismethod in which the method involves ring-opening, ring insertionmetathesis of at least one olefinic substrate and at least one cyclicolefin as the cross metathesis partner. The olefinic substrate isselected from (i) an unsaturated fatty acid or derivative thereof, (ii)an unsaturated fatty alcohol or derivative thereof, (iii) anesterification product of an unsaturated fatty acid with an alcohol, and(iv) an esterification product of a saturated fatty acid with anunsaturated alcohol. It will be appreciated that esterification productsof an unsaturated fatty acid with an alcohol include many commerciallyavailable and industrially significant compositions, e.g.,monoglycerides, diglycerides, and triglycerides such as may be found inseed oils and the like. The reaction is carried out catalytically,generally in the presence of a ruthenium alkylidene metathesis catalyst.In this embodiment, the reaction is carried out by contacting the atleast one olefinic substrate with the cross metathesis partner, i.e.,the at least one cyclic olefin, in the presence of the metathesiscatalyst under reaction conditions effective to allow ring insertioncross metathesis whereby the cyclic olefin is simultaneously opened andinserted into the olefinic substrate.

The olefinic substrate is any olefinic substrate that is suitable forthe metathesis methods disclosed herein and that is selected from: (i)an unsaturated fatty acid; (ii) an unsaturated fatty alcohol; (iii) anesterification product of an unsaturated fatty acid with an alcohol; and(iv) an esterification product of a saturated fatty acid with anunsaturated alcohol. The olefinic substrate may also be a mixture ofcompounds.

Fatty acids are organic compounds comprising a hydrophobic carbon chainsubstituted with an acid moiety at one end. The hydrophobic portion is acarbon chain that typically contains at least six carbon atoms, and maycontain up to 20 or more carbon atoms in the chain. The hydrophobiccarbon chain may be substituted or unsubstituted, may contain one ormore heteroatoms such as N, O, S or P, may contain one or morefunctional groups such as those described hereinabove, and may containone or more unsaturated regions (e.g., carbon-carbon double bonds ortriple bonds). The substituents on the hydrophobic carbon chain may beany of the substituents described hereinabove. The hydrophobic carbonchain contains an acid moiety at one end, and the acid moiety istypically a carboxylic acid. The carboxylic acid moiety may be ionized,such that it is in the form of a salt (e.g., a sodium or potassiumsalt). The carboxylic acid may also be derivitized using any of thederivitization methods typically employed for carboxylic acid compounds.For example, the carboxylic acid may be esterified via an esterificationreaction with an alcohol. Any alcohol suitable for esterification withthe fatty acid may be employed. The alcohol may be saturated orunsaturated, and may be monohydric, dihydric, or polyhydric. The alcoholmay be a C₁-C₂₀ alcohol that optionally contains one or moreheteroatoms, and optionally contains one or more substituents. Thealcohol may optionally be cyclic and/or branched. Examples of alcoholssuitable for preparing esters from the fatty acids disclosed hereininclude methanol, ethanol, propanol (e.g., isopropanol), butanol,1,2-dihydroxypropane, and glycerol.

Fatty alcohols are organic compounds comprising a hydrophobic carbonchain substituted with an alcohol moiety (i.e., —OH) at one end. Thehydrophobic carbon chain is as described for fatty acids hereinabove. Aswith fatty acids, the alcohol moiety may be ionized, such that it is inthe form of a salt (e.g., a sodium or potassium salt). Also as withfatty acids, the alcohol may be derivatized using any derivatizationmethods employed for alcohols. For example, the alcohol may be convertedto an ether via reaction with a compound containing another alcohol, ormay be converted to an ester via reaction with a compound containing acarboxylic acid. Any alcohol or ester suitable for derivatizing thefatty alcohol may be employed. Such alcohols and esters include C₁-C₂₀alcohol and esters that optionally contain one or more heteroatoms, andoptionally contain one or more substituents. The alcohols and esters mayoptionally be cyclic and/or branched. Examples of alcohols and esterssuitable for derivatizing the fatty alcohols disclosed herein includemethanol and acetic acid.

The fatty acids and fatty alcohols suitable for use as the olefinicsubstrate in the methods disclosed herein are unsaturated fatty acids orfatty acid derivatives and unsaturated fatty alcohols or fatty alcoholderivatives. That is, the olefinic substrate comprises at least oneunsaturated moiety. In one embodiment of the invention, the hydrophobiccarbon chain of the fatty acid or fatty alcohol comprises at least oneunsaturated moiety. In another embodiment of the invention, the olefinicsubstrate comprises a saturated fatty acid that is derivatized with anunsaturated compound, or the olefinic substrate comprises a saturatedfatty alcohol that is derivitized with an unsaturated compound. Forexample, a saturated fatty acid may be esterified using an unsaturatedalcohol.

Preferred unsaturated moieties are internal olefins. By “internalolefin” is meant an olefin wherein each of the olefinic carbons issubstituted by at least one non-hydrogen substituent. The non-hydrogensubstituents are selected from hydrocarbyl, substituted hydrocarbyl,heteroatom-containing hydrocarbyl, substituted heteroatom-containinghydrocarbyl, and functional groups. The internal olefin is therefore atleast disubstituted, and may further include additional non-hydrogensubstituents (e.g., a trisubstituted internal olefin). Each of thesubstituents on the internal olefinic carbons may be further substitutedas described supra. The internal olefin may be in the Z- orE-configuration. When the olefinic substrate comprises a plurality ofinternal olefins, the olefinic substrate may comprise a mixture ofinternal olefins (varying in stereochemistry and/or substituentidentity), or may comprise a plurality of identical internal olefins.

In general, the olefinic substrate may be represented by the formula(R^(I))(R^(II))C═C(R^(III))(R^(IV)), wherein R^(I), R^(II), R^(III), andR^(IV) are independently selected from H, hydrocarbyl, substitutedhydrocarbyl, heteroatom-containing hydrocarbyl, substitutedheteroatom-containing hydrocarbyl, and functional groups, provided thatat least one of R^(I) or R^(II) and at least one of R^(III) or R^(IV) isother than H. In a preferred embodiment, either R^(I) or R^(II) andeither R^(III) or R^(IV) is H, such that the internal olefin isdi-substituted.

In a preferred embodiment, the olefinic substrate is a derivative ofglycerol, and has the structure of formula (I)

wherein R^(V), R^(VI), and R^(VII) are independently selected fromhydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containinghydrocarbyl, substituted heteroatom-containing hydrocarbyl, andfunctional groups, provided that at least one of R^(V), R^(VI), andR^(VII) is other than hydrogen and comprises an internal olefin.

As an example, the olefinic substrate is a “glyceride,” and comprisesglycerol esterified with 1, 2, or 3 fatty acids, such that the olefinicsubstrate is a monoacylglycerol, diacylglycerol, or triacylglycerol(i.e., a monoglyceride, diglyceride, or triglyceride, respectively). Theolefinic substrate may also be a mixture of glycerides. Each fattyacid-derived fragment of the olefinic substrate may independently besaturated, monounsaturated, or polyunsaturated, and may furthermorederive (or be derivable) from naturally-occurring fatty acids or fromsynthetic fatty acids. Thus, the glyceride may be a compound with thestructure of formula (I), wherein R^(V), R^(VI), or R^(VII), or acombination thereof, is —C(═O)—R^(VIII), wherein R^(VIII), ishydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl,or substituted heteroatom-containing hydrocarbyl, provided that at leastone of R^(V), R^(VI), and R^(VII) contains an unsaturated moiety. As afurther example, the olefinic substrate may comprise glycerol esterifiedwith one, two, or three fatty acids that are independently selected frompalmitoleic acid, vaccenic acid, erucic acid, oleic acid,alpha-linolenic acid, gamma-linolenic acid, linoleic acid, gadoleicacid, arachidonic acid, docosahexaenoic acid (i.e., DHA),eicosapentaenoic acid (i.e., EPA), and CH₃(CH₂)_(n)COOH, where n is 2,3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or22.

The olefinic substrate may be solid (e.g., a fat) or liquid (e.g., anoil). Preferred glycerides that may be used as the olefinic substrateare seed oils and/or other vegetable oils, or are compounds that derivefrom seed oils and/or vegetable oils. Preferred oil sources includesoybean oil, sunflower oil, canola oil, safflower oil, cottonseed oil,castor oil, rapeseed oil, peanut oil, corn oil, olive oil, palm oil,sesame oil, palm kernel oil, meadowfoam oil, grape seed oil,phospholipids, phosphoglycerides, phosphatidyl ethanolamine,phosphatidyl choline, ceramides, and sphingolipids. Further preferredoils include seed oil esters, such as jojoba oil and oils from animalsources such as fish oil, butterfat, lard, tallow, chicken fat, goosefat, menhaden oil, cod liver oil, herring oil, seal oil, shark oil, andwhale oil.

The olefinic substrate may be a compound or mixture of compounds that isderived from a glyceride using any one or combination of methods wellknown in the chemical arts. Such methods include saponification,esterification, hydrogenation, isomerization, oxidation, and reduction.For example, the olefinic substrate may the carboxylic acid or mixtureof carboxylic acids that result from the saponification of amonoacylglycerol, diacylglycerol, triacylglycerol, or mixture thereof.In a preferred embodiment, the olefinic substrate is a fatty acid methylester (FAME), i.e., the methyl ester of a carboxylic acid that isderived from a glyceride. Sunflower FAME, safflower FAME, soy FAME(i.e., methyl soyate), and canola FAME are examples of such olefinicsubstrates. Additionally, olefinic substrates may include derivatives offatty acids such as oleamides, linoleamides, linolenamides, erucamideand substitution of the nitrogen with any combination of hydrogen, alkyland aryl groups.

In addition, preferred olefinic substrates include seed oil-derivedcompounds such as methyl oleate.

Preferred fatty alcohol derivatives include oleyl chloride (ie9-octadecenyl chloride), oleyl bromide, oleyl iodide, oleyl fluoride,linoleyl chloride (ie 9,12-octadecadienyl chloride), linoleyl bromide,linoleyl iodide, linoleyl fluoride, linolenyl chloride (ie9,12,15-octadecatrienyl chloride), linolenyl bromide, linolenyl iodide,linolenyl fluoride, oleyl amine, linoleyl amine, linolenyl amine, oleylthiol, linoleyl thiol, linolenyl thiol, oleyl phosphine, linoleylphosphine, linolenyl phosphine.

In addition to the olefinic substrate, described hereinabove, themetathesis reactions disclosed herein involve a cross-metathesispartner. Preferred cross-metathesis partners include cyclic olefins, andany cyclic olefin suitable for the metathesis reactions disclosed hereinmay be used. Preferred cyclic olefins include optionally substituted,optionally heteroatom-containing, mono-unsaturated, di-unsaturated, orpoly-unsaturated C₅ to C₂₄ hydrocarbons that may be mono-, di- orpoly-cyclic. The cyclic olefin may be stained or unstrained.

Preferred cyclic olefins include C₅ to C₂₄ unsaturated hydrocarbons.Also preferred are C₅ to C₂₄ cyclic hydrocarbons that contain one ormore (typically 2 to 12) heteroatoms such as O, N, S, or P. For example,crown ether cyclic olefins may include numerous 0 heteroatoms throughoutthe cycle, and these are within the scope of the invention. In addition,preferred cyclic olefins are C₅ to C₂₄ hydrocarbons that contain one ormore (typically 2 or 3) olefins. For example, the cyclic olefin may bemono-, di-, or tri-unsaturated. Examples of cyclic olefins includecyclooctene, cyclododecene, and (c,t,t)-1,5,9-cyclododecatriene.

The cyclic olefins may also comprise multiple (typically 2 or 3) rings.For example, the cyclic olefin may be mono-, di-, or tri-cyclic. Whenthe cyclic olefin comprises more than one ring, the rings may or may notbe fused. Examples of cyclic olefins that comprise multiple ringsinclude norbornene, dicyclopentadiene, and 5-ethylidene-2-norbornene.

The cyclic olefin may also be substituted—for example, a C₅ to C₂₄cyclic hydrocarbon wherein one or more (typically 2, 3, 4, or 5) of thehydrogens are replaced with non-hydrogen substituents. Suitablenon-hydrogen substituents may be chosen from the substituents describedhereinabove. For example, functionalized cyclic olefins, i.e., C₅ to C₂₄cyclic hydrocarbons wherein one or more (typically 2, 3, 4, or 5) of thehydrogens are replaced with functional groups, are within the scope ofthe invention. Suitable functional groups may be chosen from thefunctional groups described hereinabove. For example, a cyclic olefinfunctionalized with an alcohol group may be used to prepare aring-insertion product comprising pendent alcohol groups. Functionalgroups on the cyclic olefin may be protected in cases where thefunctional group interferes with the metathesis catalyst, and any of theprotecting groups commonly used in the art may be employed. Acceptableprotecting groups may be found, for example, in Greene et al.,Protective Groups in Organic Synthesis, 3^(rd) Ed. (New York: Wiley,1999). Examples of functionalized cyclic olefins include2-hydroxymethyl-5-norbornene,2-[(2-hydroxyethyl)carboxylate]-5-norbornene, Cydecanol,5-n-hexyl-2-norbornene, 5-n-butyl-2-norbornene.

Cyclic olefins incorporating any combination of the abovementionedfeatures (i.e., heteroatoms, substituents, multiple olefins, multiplerings) are suitable for the methods disclosed herein.

The cyclic olefins useful in the methods disclosed herein may bestrained or unstrained. It will be appreciated that the amount of ringstrain varies for each compound, and depends upon a number of factorsincluding the size of the ring, the presence and identity ofsubstituents, and the presence of multiple rings. Ring strain is onefactor in determining the reactivity of a molecule towards ring-openingolefin metathesis reactions. Highly strained cyclic olefins, such ascertain bicyclic compounds, readily undergo ring opening reactions witholefin metathesis catalysts. Less strained cyclic olefins, such ascertain unsubstituted hydrocarbon monocyclic olefins, are generally lessreactive to such reactions. It should be noted, however, that in somecases, ring opening reactions of relatively unstrained (and thereforerelatively unreactive) cyclic olefins becomes possible when performed inthe presence of the olefinic substrates disclosed herein.

A plurality of cyclic olefins may be used as the cross-metathesispartner with the olefinic substrate. For example, two cyclic olefinsselected from the cyclic olefins described hereinabove may be employedin order to form metathesis products that incorporate both cyclicolefins. Where two or more cyclic olefins are used, one example of apreferred second cyclic olefin is a cyclic alkenol, i.e., a C₅-C₂₄cyclic hydrocarbon wherein at least one of the hydrogen substituents isreplaced with an alcohol or protected alcohol moiety to yield afunctionalized cyclic olefin.

The use of a plurality of cyclic olefins, and in particular when atleast one of the cyclic olefins is functionalized, allows for furthercontrol over the positioning of functional groups within the products.For example, the density of cross-linking points can be controlled inpolymers and macromonomers prepared using the methods disclosed herein.Control over the quantity and density of substituents and functionalgroups also allows for control over the physical properties (e.g.,melting point, tensile strength, glass transition temperature, etc.) ofthe products. Control over these and other properties is possible forreactions using only a single cyclic olefin, but it will be appreciatedthat the use of a plurality of cyclic olefins further enhances the rangeof possible metathesis products.

A ring insertion reaction is carried out by contacting the at least oneolefinic substrate with the cross metathesis partner, i.e., the at leastone cyclic olefin, in the presence of the metathesis catalyst underreaction conditions effective to allow ring insertion cross metathesiswhereby the cyclic olefin is simultaneously opened and inserted into theolefinic substrate. Examples are illustrated in Schemes 3, 4, and 5 inwhich an olefinic substrate is reacted with a cyclic olefin to producemetathesis products.

In Scheme 3 and Scheme 4, the ring insertion cross metathesis reactionsare carried out using seed oils as the olefinic substrates to producechain extended trialkylglycerides (TAGs) and chain extended fatty acidmethyl esters (FAMEs). The metathesis products shall, however, not belimited to these specific products and can include any mixtures of chainextended fatty acid components, mixtures of chain extended olefincomponents, and mixtures of chain extended diacid components.

An illustration of a ring opening cross metathesis reaction in which acycloalkene and a cyclic alkenol are employed is provided in Scheme 5.The product from the reaction shown in scheme 5 is a copolymer thatcontains pendent alcohol groups dispersed throughout the backbone. Itwill be appreciated that the spacing between alcohol groups along theproduct polymer backbone will be dependent upon the relative amounts ofcyclic olefin and cyclic alkenol that are incorporated into the polymer.Therefore, relative amounts of cyclic olefin and cyclic alkenol added tothe reaction mixture is one way in which this spacing can be controlled.

The reactions disclosed herein are catalyzed by any of the metathesiscatalysts that are described infra. The catalyst is typically added tothe reaction medium as a solid, but may also be added as a solutionwherein the catalyst is dissolved in an appropriate solvent, or as asuspension wherein the catalyst is suspended in an appropriate liquid.It will be appreciated that the amount of catalyst that is used (i.e.,the “catalyst loading”) in the reaction is dependent upon a variety offactors such as the identity of the reactants and the reactionconditions that are employed. It is therefore understood that catalystloading may be optimally and independently chosen for each reaction. Ingeneral, however, the catalyst will be present in an amount that rangesfrom a low of about 0.1 ppm, 1 ppm, or 5 ppm, to a high of about 10 ppm,15 ppm, 25 ppm, 50 ppm, 100 ppm, 200 ppm, 500 ppm, or 1000 ppm relativeto the amount of the olefinic substrate. Catalyst loading, when measuredin ppm relative to the amount of the olefinic substrate, is calculatedusing the equation

${{ppm}\mspace{14mu}{catalyst}} = {\frac{{moles}\mspace{14mu}{catalyst}}{{moles}\mspace{14mu}{olefinic}\mspace{14mu}{substrate}}*1\text{,}000\text{,}000.}$Alternatively, the amount of catalyst can be measured in terms of mol %relative to the amount of olefinic substrate, using the equation

${{mol}\mspace{14mu}\%\mspace{14mu}{catalyst}} = {\frac{{moles}\mspace{14mu}{catalyst}}{{moles}\mspace{14mu}{olefinic}\mspace{14mu}{substrate}}*100.}$Thus, the catalyst will generally be present in an amount that rangesfrom a low of about 0.00001 mol %, 0.0001 mol %, or 0.0005 mol %, to ahigh of about 0.001 mol %, 0.0015 mol %, 0.0025 mol %, 0.005 mol %, 0.01mol %, 0.02 mol %, 0.05 mol %, or 0.1 mol % relative to the olefinicsubstrate.

In a preferred embodiment, the reactions disclosed herein are carriedout under a dry, inert atmosphere. Such an atmosphere may be createdusing any inert gas, including such gases as nitrogen and argon. The useof an inert atmosphere is optimal in terms of promoting catalystactivity, and reactions performed under an inert atmosphere typicallyare performed with relatively low catalyst loading. The reactionsdisclosed herein may also be carried out in an oxygen-containing and/ora water-containing atmosphere, and in one embodiment, the reactions arecarried out under ambient conditions. The presence of oxygen or water inthe reaction may, however, necessitate the use of higher catalystloadings as compared with reactions performed under an inert atmosphere.

Where the vapor pressure of the reactants allows, the reactionsdisclosed herein may also be carried out under reduced pressure.

The olefin metathesis catalyst for carrying out the reactions disclosedherein is preferably a Group 8 transition metal complex having thestructure of formula (II)

in which the various substituents are as follows.

M is a Group 8 transition metal;

L¹, L² and L³ are neutral electron donor ligands;

n is 0 or 1, such that L³ may or may not be present;

m is 0, 1, or 2;

X¹ and X² are anionic ligands; and

R¹ and R² are independently selected from hydrogen, hydrocarbyl,substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substitutedheteroatom-containing hydrocarbyl, and functional groups,

wherein any two or more of X¹, X², L¹, L², L³, R¹, and R² can be takentogether to form one or more cyclic groups, and further wherein any oneor more of X¹, X², L¹, L², L³, R¹, and R² may be attached to a support.

Preferred catalysts contain Ru or Os as the Group 8 transition metal,with Ru particularly preferred.

Numerous embodiments of the catalysts useful in the reactions disclosedherein are described in more detail infra. For the sake of convenience,the catalysts are described in groups, but it should be emphasized thatthese groups are not meant to be limiting in any way. That is, any ofthe catalysts useful in the invention may fit the description of morethan one of the groups described herein.

A first group of catalysts, then, are commonly referred to as FirstGeneration Grubbs-type catalysts, and have the structure of formula(II). For the first group of catalysts, M and m are as described above,and n, X¹, X², L¹, L², L³, R¹, and R² are described as follows.

For the first group of catalysts, n is 0, and L¹ and L² areindependently selected from phosphine, sulfonated phosphine, phosphite,phosphinite, phosphonite, arsine, stibine, ether, amine, amide, imine,sulfoxide, carboxyl, nitrosyl, pyridine, substituted pyridine,imidazole, substituted imidazole, pyrazine, and thioether. Exemplaryligands are trisubstituted phosphines.

X¹ and X² are anionic ligands, and may be the same or different, or arelinked together to form a cyclic group, typically although notnecessarily a five- to eight-membered ring. In preferred embodiments, X¹and X² are each independently hydrogen, halide, or one of the followinggroups: C₁-C₂₀ alkyl, C₅-C₂₄ aryl, C₁-C₂₀ alkoxy, C₅-C₂₄ aryloxy, C₂-C₂₀alkoxycarbonyl, C₆-C₂₄ aryloxycarbonyl, C₂-C₂₄ acyl, C₂-C₂₄ acyloxy,C₁-C₂₀ alkylsulfonato, C₅-C₂₄ arylsulfonato, C₁-C₂₀ alkylsulfanyl,C₅-C₂₄ arylsulfanyl, C₁-C₂₀ alkylsulfinyl, or C₅-C₂₄ arylsulfinyl.Optionally, X¹ and X² may be substituted with one or more moietiesselected from C₁-C₁₂ alkyl, C₁-C₁₂ alkoxy, C₅-C₂₄ aryl, and halide,which may, in turn, with the exception of halide, be further substitutedwith one or more groups selected from halide, C₁-C₆ alkyl, C₁-C₆ alkoxy,and phenyl. In more preferred embodiments, X¹ and X² are halide,benzoate, C₂-C₆ acyl, C₂-C₆ alkoxycarbonyl, C₁-C₆ alkyl, phenoxy, C₁-C₆alkoxy, C₁-C₆ alkylsulfanyl, aryl, or C₁-C₆ alkylsulfonyl. In even morepreferred embodiments, X¹ and X² are each halide, CF₃CO₂, CH₃CO₂,CFH₂CO₂, (CH₃)₃CO, (CF₃)₂(CH₃)CO, (CF₃)(CH₃)₂CO, PhO, MeO, EtO,tosylate, mesylate, or trifluoromethane-sulfonate. In the most preferredembodiments, X¹ and X² are each chloride.

R¹ and R² are independently selected from hydrogen, hydrocarbyl (e.g.,C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl, C₅-C₂₄ aryl, C₆-C₂₄alkaryl, C₆-C₂₄ aralkyl, etc.), substituted hydrocarbyl (e.g.,substituted C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl, C₅-C₂₄ aryl,C₆-C₂₄ alkaryl, C₆-C₂₄ aralkyl, etc.), heteroatom-containing hydrocarbyl(e.g., heteroatom-containing C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, C₂-C₂₀alkynyl, C₅-C₂₄ aryl, C₆-C₂₄ alkaryl, C₆-C₂₄ aralkyl, etc.), andsubstituted heteroatom-containing hydrocarbyl (e.g., substitutedheteroatom-containing C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl,C₅-C₂₄ aryl, C₆-C₂₄ alkaryl, C₆-C₂₄ aralkyl, etc.), and functionalgroups. R¹ and R² may also be linked to form a cyclic group, which maybe aliphatic or aromatic, and may contain substituents and/orheteroatoms. Generally, such a cyclic group will contain 4 to 12,preferably 5, 6, 7, or 8 ring atoms.

In preferred catalysts, R¹ is hydrogen and R² is selected from C₁-C₂₀alkyl, C₂-C₂₀ alkenyl, and C₅-C₂₄ aryl, more preferably C₁-C₆ alkyl,C₂-C₆ alkenyl, and C₅-C₁₄ aryl. Still more preferably, R² is phenyl,vinyl, methyl, isopropyl, or t-butyl, optionally substituted with one ormore moieties selected from C₁-C₆ alkyl, C₁-C₆ alkoxy, phenyl, and afunctional group Fn as defined earlier herein. Most preferably, R² isphenyl or vinyl substituted with one or more moieties selected frommethyl, ethyl, chloro, bromo, iodo, fluoro, nitro, dimethylamino,methyl, methoxy, and phenyl. Optimally, R² is phenyl or —C═C(CH₃)₂.

Any two or more (typically two, three, or four) of X¹, X², L¹, L², L³,R¹, and R² can be taken together to form a cyclic group, as disclosed,for example, in U.S. Pat. No. 5,312,940 to Grubbs et al. When any of X¹,X², L¹, L², L³, R¹, and R² are linked to form cyclic groups, thosecyclic groups may contain 4 to 12, preferably 4, 5, 6, 7 or 8 atoms, ormay comprise two or three of such rings, which may be either fused orlinked. The cyclic groups may be aliphatic or aromatic, and may beheteroatom-containing and/or substituted. The cyclic group may, in somecases, form a bidentate ligand or a tridentate ligand. Examples ofbidentate ligands include, but are not limited to, bisphosphines,dialkoxides, alkyldiketonates, and aryldiketonates.

A second group of catalysts, commonly referred to as Second GenerationGrubbs-type catalysts, have the structure of formula (II), wherein L¹ isa carbene ligand having the structure of formula (III)

such that the complex may have the structure of formula (IV)

wherein M, m, n, X¹, X², L², L³, R¹, and R² are as defined for the firstgroup of catalysts, and the remaining substituents are as follows.

X and Y are heteroatoms typically selected from N, O, S, and P. Since Oand S are divalent, p is necessarily zero when X is O or S, and q isnecessarily zero when Y is O or S. However, when X is N or P, then p is1, and when Y is N or P, then q is 1. In a preferred embodiment, both Xand Y are N.

Q¹, Q², Q³, and Q⁴ are linkers, e.g., hydrocarbylene (includingsubstituted hydrocarbylene, heteroatom-containing hydrocarbylene, andsubstituted heteroatom-containing hydrocarbylene, such as substitutedand/or heteroatom-containing alkylene) or —(CO)—, and w, x, y, and z areindependently zero or 1, meaning that each linker is optional.Preferably, w, x, y, and z are all zero. Further, two or moresubstituents on adjacent atoms within Q¹, Q², Q³, and Q⁴ may be linkedto form an additional cyclic group.

R³, R^(3A), R⁴, and R^(4A) are independently selected from hydrogen,hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl,and substituted heteroatom-containing hydrocarbyl.

In addition, any two or more of X¹, X², L¹, L², L³, R¹, R², R³, R^(3A),R⁴, and R^(4A) can be taken together to form a cyclic group, and any oneor more of X¹, X², L¹, L², L³, R¹, R², R³, R^(3A), R⁴, and R^(4A) may beattached to a support.

Preferably, R^(3A) and R^(4A) are linked to form a cyclic group so thatthe carbene ligand has the structure of formula (V)

wherein R³ and R⁴ are defined above, with preferably at least one of R³and R⁴, and more preferably both R³ and R⁴, being alicyclic or aromaticof one to about five rings, and optionally containing one or moreheteroatoms and/or substituents. Q is a linker, typically ahydrocarbylene linker, including substituted hydrocarbylene,heteroatom-containing hydrocarbylene, and substitutedheteroatom-containing hydrocarbylene linkers, wherein two or moresubstituents on adjacent atoms within Q may also be linked to form anadditional cyclic structure, which may be similarly substituted toprovide a fused polycyclic structure of two to about five cyclic groups.Q is often, although again not necessarily, a two-atom linkage or athree-atom linkage.

Examples of N-heterocyclic carbene ligands suitable as L¹ thus include,but are not limited to, the following:

When M is ruthenium, then, the preferred complexes have the structure offormula (VI)

In a more preferred embodiment, Q is a two-atom linkage having thestructure —CR¹¹R¹²—CR¹³R¹⁴— or —CR¹¹═CR¹³—, preferably—CR¹¹R¹²—CR¹³R¹⁴—, wherein R¹¹, R¹², R¹³, and R¹⁴ are independentlyselected from hydrogen, hydrocarbyl, substituted hydrocarbyl,heteroatom-containing hydrocarbyl, substituted heteroatom-containinghydrocarbyl, and functional groups. Examples of functional groups hereinclude carboxyl, C₁-C₂₀ alkoxy, C₅-C₂₄ aryloxy, C₂-C₂₀ alkoxycarbonyl,C₅-C₂₄ alkoxycarbonyl, C₂-C₂₄ acyloxy, C₁-C₂₀ alkylthio, C₅-C₂₄arylthio, C₁-C₂₀ alkylsulfonyl, and C₁-C₂₀ alkylsulfinyl, optionallysubstituted with one or more moieties selected from C₁-C₁₂ alkyl, C₁-C₁₂alkoxy, C₅-C₁₄ aryl, hydroxyl, sulfhydryl, formyl, and halide. R¹¹, R¹²,R¹³, and R¹⁴ are preferably independently selected from hydrogen, C₁-C₁₂alkyl, substituted C₁-C₁₂ alkyl, C₁-C₁₂ heteroalkyl, substituted C₁-C₁₂heteroalkyl, phenyl, and substituted phenyl. Alternatively, any two ofR¹¹, R¹², R¹³, and R¹⁴ may be linked together to form a substituted orunsubstituted, saturated or unsaturated ring structure, e.g., a C₄-C₁₂alicyclic group or a C₅ or C₆ aryl group, which may itself besubstituted, e.g., with linked or fused alicyclic or aromatic groups, orwith other substituents.

When R³ and R⁴ are aromatic, they are typically although not necessarilycomposed of one or two aromatic rings, which may or may not besubstituted, e.g., R³ and R⁴ may be phenyl, substituted phenyl,biphenyl, substituted biphenyl, or the like. In one preferredembodiment, R³ and R⁴ are the same and are each unsubstituted phenyl orphenyl substituted with up to three substituents selected from C₁-C₂₀alkyl, substituted C₁-C₂₀ alkyl, C₁-C₂₀ heteroalkyl, substituted C₁-C₂₀heteroalkyl, C₅-C₂₄ aryl, substituted C₅-C₂₄ aryl, C₅-C₂₄ heteroaryl,C₆-C₂₄ aralkyl, C₆-C₂₄ alkaryl, or halide. Preferably, any substituentspresent are hydrogen, C₁-C₁₂ alkyl, C₁-C₁₂ alkoxy, C₅-C₁₄ aryl,substituted C₅-C₁₄ aryl, or halide. As an example, R³ and R⁴ aremesityl.

In a third group of catalysts having the structure of formula (II), M,m, n, X¹, X², R¹, and R² are as defined for the first group ofcatalysts, L¹ is a strongly coordinating neutral electron donor ligandsuch as any of those described for the first and second group ofcatalysts, and L² and L³ are weakly coordinating neutral electron donorligands in the form of optionally substituted heterocyclic groups.Again, n is zero or 1, such that L³ may or may not be present.Generally, in the third group of catalysts, L² and L³ are optionallysubstituted five- or six-membered monocyclic groups containing 1 to 4,preferably 1 to 3, most preferably 1 to 2 heteroatoms, or are optionallysubstituted bicyclic or polycyclic structures composed of 2 to 5 suchfive- or six-membered monocyclic groups. If the heterocyclic group issubstituted, it should not be substituted on a coordinating heteroatom,and any one cyclic moiety within a heterocyclic group will generally notbe substituted with more than 3 substituents.

For the third group of catalysts, examples of L² and L³ include, withoutlimitation, heterocycles containing nitrogen, sulfur, oxygen, or amixture thereof.

Examples of nitrogen-containing heterocycles appropriate for L² and L³include pyridine, bipyridine, pyridazine, pyrimidine, bipyridamine,pyrazine, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, pyrrole,2H-pyrrole, 3H-pyrrole, pyrazole, 2H-imidazole, 1,2,3-triazole,1,2,4-triazole, indole, 3H-indole, 1H-isoindole, cyclopenta(b)pyridine,indazole, quinoline, bisquinoline, isoquinoline, bisisoquinoline,cinnoline, quinazoline, naphthyridine, piperidine, piperazine,pyrrolidine, pyrazolidine, quinuclidine, imidazolidine, picolylimine,purine, benzimidazole, bisimidazole, phenazine, acridine, and carbazole.

Examples of sulfur-containing heterocycles appropriate for L² and L³include thiophene, 1,2-dithiole, 1,3-dithiole, thiepin,benzo(b)thiophene, benzo(c)thiophene, thionaphthene, dibenzothiophene,2H-thiopyran, 4H-thiopyran, and thioanthrene.

Examples of oxygen-containing heterocycles appropriate for L² and L³include 2H-pyran, 4H-pyran, 2-pyrone, 4-pyrone, 1,2-dioxin, 1,3-dioxin,oxepin, furan, 2H-1-benzopyran, coumarin, coumarone, chromene,chroman-4-one, isochromen-1-one, isochromen-3-one, xanthene,tetrahydrofuran, 1,4-dioxan, and dibenzofuran.

Examples of mixed heterocycles appropriate for L² and L³ includeisoxazole, oxazole, thiazole, isothiazole, 1,2,3-oxadiazole,1,2,4-oxadiazole, 1,3,4-oxadiazole, 1,2,3,4-oxatriazole,1,2,3,5-oxatriazole, 3H-1,2,3-dioxazole, 3H-1,2-oxathiole,1,3-oxathiole, 4H-1,2-oxazine, 2H-1,3-oxazine, 1,4-oxazine,1,2,5-oxathiazine, o-isooxazine, phenoxazine, phenothiazine,pyrano[3,4-b]pyrrole, indoxazine, benzoxazole, anthranil, andmorpholine.

Preferred L² and L³ ligands are aromatic nitrogen-containing andoxygen-containing heterocycles, and particularly preferred L² and L³ligands are monocyclic N-heteroaryl ligands that are optionallysubstituted with 1 to 3, preferably 1 or 2, substituents. Specificexamples of particularly preferred L² and L³ ligands are pyridine andsubstituted pyridines, such as 3-bromopyridine, 4-bromopyridine,3,5-dibromopyridine, 2,4,6-tribromopyridine, 2,6-dibromopyridine,3-chloropyridine, 4-chloropyridine, 3,5-dichloropyridine,2,4,6-trichloropyridine, 2,6-dichloropyridine, 4-iodopyridine,3,5-diiodopyridine, 3,5-dibromo-4-methylpyridine,3,5-dichloro-4-methylpyridine, 3,5-dimethyl-4-bromopyridine,3,5-dimethylpyridine, 4-methylpyridine, 3,5-diisopropylpyridine,2,4,6-trimethylpyridine, 2,4,6-triisopropylpyridine,4-(tert-butyl)pyridine, 4-phenylpyridine, 3,5-diphenylpyridine,3,5-dichloro-4-phenylpyridine, and the like.

In general, any substituents present on L² and/or L³ are selected fromhalo, C₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, C₁-C₂₀ heteroalkyl,substituted C₁-C₂₀ heteroalkyl, C₅-C₂₄ aryl, substituted C₅-C₂₄ aryl,C₅-C₂₄ heteroaryl, substituted C₅-C₂₄ heteroaryl, C₆-C₂₄ alkaryl,substituted C₆-C₂₄ alkaryl, C₆-C₂₄ heteroalkaryl, substituted C₆-C₂₄heteroalkaryl, C₆-C₂₄ aralkyl, substituted C₆-C₂₄ aralkyl, C₆-C₂₄heteroaralkyl, substituted C₆-C₂₄ heteroaralkyl, and functional groups,with suitable functional groups including, without limitation, C₁-C₂₀alkoxy, C₅-C₂₄ aryloxy, C₂-C₂₀ alkylcarbonyl, C₆-C₂₄ arylcarbonyl,C₂-C₂₀ alkylcarbonyloxy, C₆-C₂₄ arylcarbonyloxy, C₂-C₂₀ alkoxycarbonyl,C₆-C₂₄ aryloxycarbonyl, halocarbonyl, C₂-C₂₀ alkylcarbonato, C₆-C₂₄arylcarbonato, carboxy, carboxylato, carbamoyl, mono-(C₁-C₂₀alkyl)-substituted carbamoyl, di-(C₁-C₂₀ alkyl)-substituted carbamoyl,di-N—(C₁-C₂₀ alkyl), N—(C₅-C₂₄ aryl)-substituted carbamoyl, mono-(C₅-C₂₄aryl)-substituted carbamoyl, di-(C₆-C₂₄ aryl)-substituted carbamoyl,thiocarbamoyl, mono-(C₁-C₂₀ alkyl)-substituted thiocarbamoyl, di-(C₁-C₂₀alkyl)-substituted thiocarbamoyl, di-N—(C₁-C₂₀ alkyl)-N—(C₆-C₂₄aryl)-substituted thiocarbamoyl, mono-(C₆-C₂₄ aryl)-substitutedthiocarbamoyl, di-(C₆-C₂₄ aryl)-substituted thiocarbamoyl, carbamido,formyl, thioformyl, amino, mono-(C₁-C₂₀ alkyl)-substituted amino,di-(C₁-C₂₀ alkyl)-substituted amino, mono-(C₅-C₂₄ aryl)-substitutedamino, di-(C₅-C₂₄ aryl)-substituted amino, di-N—(C₁-C₂₀ alkyl),N—(C₅-C₂₄ aryl)-substituted amino, C₂-C₂₀ alkylamido, C₆-C₂₄ arylamido,imino, C₁-C₂₀ alkylimino, C₅-C₂₄ arylimino, nitro, and nitroso. Inaddition, two adjacent substituents may be taken together to form aring, generally a five- or six-membered alicyclic or aryl ring,optionally containing 1 to 3 heteroatoms and 1 to 3 substituents asabove.

Preferred substituents on L and L³ include, without limitation, halo,C₁-C₁₂ alkyl, substituted C₁-C₁₂ alkyl, C₁-C₁₂ heteroalkyl, substitutedC₁-C₁₂ heteroalkyl, C₅-C₁₄ aryl, substituted C₅-C₁₄ aryl, C₅-C₁₄heteroaryl, substituted C₅-C₁₄ heteroaryl, C₆-C₁₆ alkaryl, substitutedC₆-C₁₆ alkaryl, C₆-C₁₆ heteroalkaryl, substituted C₆-C₁₆ heteroalkaryl,C₆-C₁₆ aralkyl, substituted C₆-C₁₆ aralkyl, C₆-C₁₆ heteroaralkyl,substituted C₆-C₁₆ heteroaralkyl, C₁-C₁₂ alkoxy, C₅-C₁₄ aryloxy, C₂-C₁₂alkylcarbonyl, C₆-C₁₄ arylcarbonyl, C₂-C₁₂ alkylcarbonyloxy, C₆-C₁₄arylcarbonyloxy, C₂-C₁₂ alkoxycarbonyl, C₆-C₁₄ aryloxycarbonyl,halocarbonyl, formyl, amino, mono-(C₁-C₁₂ alkyl)-substituted amino,di-(C₁-C₁₂ alkyl)-substituted amino, mono-(C₅-C₁₄ aryl)-substitutedamino, di-(C₅-C₁₄ aryl)-substituted amino, and nitro.

Of the foregoing, the most preferred substituents are halo, C₁-C₆ alkyl,C₁-C₆ haloalkyl, C₁-C₆ alkoxy, phenyl, substituted phenyl, formyl,N,N-diC₁-C₆ alkyl)amino, nitro, and nitrogen heterocycles as describedabove (including, for example, pyrrolidine, piperidine, piperazine,pyrazine, pyrimidine, pyridine, pyridazine, etc.).

L² and L³ may also be taken together to form a bidentate or multidentateligand containing two or more, generally two, coordinating heteroatomssuch as N, O, S, or P, with preferred such ligands being diimine ligandsof the Brookhart type. One representative bidentate ligand has thestructure of formula (VII)

wherein R¹⁵, R¹⁶, R¹⁷, and R¹⁸ hydrocarbyl (e.g., C₁-C₂₀ alkyl, C₂-C₂₀alkenyl, C₂-C₂₀ alkynyl, C₅-C₂₄ aryl, C₆-C₂₄ alkaryl, or C₆-C₂₄aralkyl), substituted hydrocarbyl (e.g., substituted C₁-C₂₀ alkyl,C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl, C₅-C₂₄ aryl, C₆-C₂₄ alkaryl, or C₆-C₂₄aralkyl), heteroatom-containing hydrocarbyl (e.g., C₁-C₂₀ heteroalkyl,C₅-C₂₄ heteroaryl, heteroatom-containing C₆-C₂₄ aralkyl, orheteroatom-containing C₆-C₂₄ alkaryl), or substitutedheteroatom-containing hydrocarbyl (e.g., substituted C₁-C₂₀ heteroalkyl,C₅-C₂₄ heteroaryl, heteroatom-containing C₆-C₂₄ aralkyl, orheteroatom-containing C₆-C₂₄ alkaryl), or (1) R¹⁵ and R¹⁶, (2) R¹⁷ andR¹⁸, (3) R¹⁶ and R¹⁷, or (4) both R¹⁵ and R¹⁶, and R¹⁷ and R¹⁸, may betaken together to form a ring, i.e., an N-heterocycle. Preferred cyclicgroups in such a case are five- and six-membered rings, typicallyaromatic rings.

In a fourth group of catalysts that have the structure of formula (I),two of the substituents are taken together to form a bidentate ligand ora tridentate ligand. Examples of bidentate ligands include, but are notlimited to, bisphosphines, dialkoxides, alkyldiketonates, andaryldiketonates. Specific examples include —P(Ph)₂CH₂CH₂P(Ph)₂-,—As(Ph)₂CH₂CH₂As(Ph₂)—, —P(Ph)₂CH₂CH₂C(CF₃)₂O—, binaphtholate dianions,pinacolate dianions, —P(CH₃)₂(CH₂)₂P(CH₃)₂—, and —OC(CH₃)₂(CH₃)₂CO—.Preferred bidentate ligands are —P(Ph)₂ CH₂CH₂P(Ph)₂- and—P(CH₃)₂(CH₂)₂P(CH₃)₂—. Tridentate ligands include, but are not limitedto, (CH₃)₂ NCH₂CH₂P(Ph)CH₂CH₂N(CH₃)₂. Other preferred tridentate ligandsare those in which any three of X¹, X², L¹, L², L³, R¹, and R² (e.g.,X¹, L¹, and L²) are taken together to be cyclopentadienyl, indenyl, orfluorenyl, each optionally substituted with C₂-C₂₀ alkenyl, C₂-C₂₀alkynyl, C₁-C₂₀ alkyl, C₅-C₂₀ aryl, C₁-C₂₀ alkoxy, C₂-C₂₀ alkenyloxy,C₂-C₂₀ alkynyloxy, C₅-C₂₀ aryloxy, C₂-C₂₀ alkoxycarbonyl, C₁-C₂₀alkylthio, C₁-C₂₀ alkylsulfonyl, or C₁-C₂₀ alkylsulfinyl, each of whichmay be further substituted with C₁-C₆ alkyl, halide, C₁-C₆ alkoxy orwith a phenyl group optionally substituted with halide, C₁-C₆ alkyl, orC₁-C₆ alkoxy. More preferably, in compounds of this type, X, L¹, and L²are taken together to be cyclopentadienyl or indenyl, each optionallysubstituted with vinyl, C₁-C₁₀ alkyl, C₅-C₂₀ aryl, C₁-C₁₀ carboxylate,C₂-C₁₀ alkoxycarbonyl, C₁-C₁₀ alkoxy, or C₅-C₂₀ aryloxy, each optionallysubstituted with C₁-C₆ alkyl, halide, C₁-C₆ alkoxy or with a phenylgroup optionally substituted with halide, C₁-C₆ alkyl or C₁-C₆ alkoxy.Most preferably, X, L¹ and L² may be taken together to becyclopentadienyl, optionally substituted with vinyl, hydrogen, methyl,or phenyl. Tetradentate ligands include, but are not limited toO₂C(CH₂)₂P(Ph)(CH₂)₂P(Ph)(CH₂)₂CO₂, phthalocyanines, and porphyrins.

Complexes wherein L² and R² are linked are examples of the fourth groupof catalysts, and are commonly called “Grubbs-Hoveyda” catalysts.Examples of Grubbs-Hoveyda-type catalysts include the following:

wherein L¹, X¹, X², and M are as described for any of the other groupsof catalysts.

In addition to the catalysts that have the structure of formula (II), asdescribed above, other transition metal carbene complexes include, butare not limited to:

neutral ruthenium or osmium metal carbene complexes containing metalcenters that are formally in the +2 oxidation state, have an electroncount of 16, are penta-coordinated, and are of the general formula(VIII);

neutral ruthenium or osmium metal carbene complexes containing metalcenters that are formally in the +2 oxidation state, have an electroncount of 18, are hexa-coordinated, and are of the general formula (IX);

cationic ruthenium or osmium metal carbene complexes containing metalcenters that are formally in the +2 oxidation state, have an electroncount of 14, are tetra-coordinated, and are of the general formula (X);and

cationic ruthenium or osmium metal carbene complexes containing metalcenters that are formally in the +2 oxidation state, have an electroncount of 14, are penta-coordinated, and are of the general formula (XI)

wherein: X¹, X², L¹, L², n, L¹, R¹, and R² are as defined for any of thepreviously defined four groups of catalysts; r and s are independentlyzero or 1; t is an integer in the range of zero to 5; Y is anynon-coordinating anion (e.g., a halide ion, BF₄ ⁻, etc.); Z¹ and Z² areindependently selected from —O—, —S—, —NR²—, —PR²—, —P(═O)R²—, —P(OR²)—,—P(═O)(OR²)—, —C(═O)—, —C(═O)O—, —OC(═O)—, —OC(═O)O—, —S(═O)—, and—S(═O)₂—; Z³ is any cationic moiety such as —P(R²)₃ ⁺ or —N(R²)₃ ⁺; andany two or more of X¹, X², L¹, L², L³, n, Z¹, Z², Z³, R¹, and R² may betaken together to form a cyclic group, e.g., a multidentate ligand, andwherein any one or more of X¹, X², L¹, L², n, L³, Z¹, Z², Z³, R¹, and R²may be attached to a support.

As is understood in the field of catalysis, suitable solid supports forany of the catalysts described herein may be of synthetic,semi-synthetic, or naturally occurring materials, which may be organicor inorganic, e.g., polymeric, ceramic, or metallic. Attachment to thesupport will generally, although not necessarily, be covalent, and thecovalent linkage may be direct or indirect, if indirect, typicallythrough a functional group on a support surface.

Non-limiting examples of catalysts that may be used in the reactionsdisclosed herein include the following, some of which for convenienceare identified throughout this disclosure by reference to theirmolecular weight:

In the foregoing molecular structures and formulae, Ph representsphenyl, Cy represents cyclohexyl, Me represents methyl, nBu representsn-butyl, i-Pr represents isopropyl, py represents pyridine (coordinatedthrough the N atom), and Mes represents mesityl (i.e.,2,4,6-trimethylphenyl).

Further examples of catalysts useful in the reactions disclosed hereininclude the following: ruthenium (II)dichloro(3-methyl-1,2-butenylidene) bis(tricyclopentylphosphine) (C716);ruthenium (II) dichloro(3-methyl-1,2-butenylidene)bis(tricyclohexylphosphine) (C801); ruthenium (II)dichloro(phenylmethylene) bis(tricyclohexylphosphine) (C823); ruthenium(II) [1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene) dichloro(phenylmethylene) (triphenylphosphine) (C830), and ruthenium (II)dichloro(vinyl phenylmethylene) bis(tricyclohexylphosphine) (C835);ruthenium (II) dichloro (tricyclohexylphosphine)(o-isopropoxyphenylmethylene) (C601), and ruthenium (II)(1,3-bis-(2,4,6,-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene) (bis 3-bromopyridine (C884)).

Still further catalysts useful in the ring-opening cross-methathesis(ROCM) reactions disclosed herein include the following, identified asstructures 60-68:

The transition metal complexes used as catalysts herein can be preparedby several different methods, such as those described by Schwab et al.(1996) J. Am. Chem. Soc. 118: 100-110, Scholl et al. (1999) Org. Lett.6:953-956, Sanford et al. (2001) J. Am. Chem. Soc. 123:749-750, U.S.Pat. No. 5,312,940 and U.S. Pat. No. 5,342,909. Also see U.S. PatentPublication No. 2003/0055262 to Grubbs et al. filed Apr. 16, 2002 for“Group 8 Transition Metal Carbene Complexes as Enantioselective OlefinMetathesis Catalysts”, International Patent Publication No. WO 02/079208application Ser. No. 10/115,581 to Grubbs, Morgan, Benitez, and Louie,filed Apr. 2, 2002, for “One-Pot Synthesis of Group 8 Transition MetalCarbene Complexes Useful as Olefin Metathesis Catalysts,” commonlyassigned herewith to the California Institute of Technology. Preferredsynthetic methods are described in International Patent Publication No.WO 03/11455A1 to Grubbs et al. for “Hexacoordinated Ruthenium or OsmiumMetal Carbene Metathesis Catalysts,” published Feb. 13, 2003.

The components of the reactions disclosed herein may be combined in anyorder, and it will be appreciated that the order of combining thereactants may be adjusted as needed. For example, the olefinic substratemay be added to the cross-metathesis partner, followed by addition ofthe catalyst. Alternatively, the olefinic substrate and cross-metathesispartner may be added to the catalyst. When one of the reactants is agas, it may be necessary to add the catalyst to the liquid or solidreactant before introducing the gaseous reactant.

The catalyst may be added to the reaction either as a solid, dissolvedin one of the reactants, or dissolved in a solvent.

The reactions disclosed herein may be carried out in a solvent, and anysolvent that is inert towards cross-metathesis may be employed.Generally, solvents that may be used in the cross-metathesis reactionsinclude organic, protic, or aqueous solvents, such as aromatichydrocarbons, chlorinated hydrocarbons, ethers, aliphatic hydrocarbons,alcohols, water, or mixtures thereof. Example solvents include benzene,toluene, p-xylene, methylene chloride, 1,2-dichloroethane,dichlorobenzene, chlorobenzene, tetrahydrofuran, diethylether, pentane,methanol, ethanol, water, or mixtures thereof. In a preferredembodiment, the reactions disclosed herein are carried out neat, i.e.,without the use of a solvent.

It will be appreciated that the temperature at which a cross-metathesisreaction according to methods disclosed herein is conducted can beadjusted as needed, and may be at least about −78° C., −40° C., −10° C.,0° C., 10° C., 20° C., 25° C., 35° C., 50° C., 70° C., 100° C., or 150°C., or the temperature may be in a range that has any of these values asthe upper or lower bounds. In a preferred embodiment, the reactions arecarried out at a temperature of at least about 35° C., and in anotherpreferred embodiment, the reactions are carried out at a temperature ofat least about 50° C.

It will further be appreciated that the molar ratio of the reactantswill be dependent upon the identities of the reactants and the desiredproducts. Although the cyclic olefin and the olefinic substrate may beused in equal molar amounts, in general, an excess of cyclic olefin withrespect to the olefinic substrate will be present. For example, themolar ratio of the cyclic olefin (as the sum of all compounds when thecyclic olefin comprises a plurality of cyclic compounds) to the olefinicsubstrate may be up to 2:1, 5:1, 10:1, 25:1, 50:1, 100:1, 250:1, 500:1,1000:1, 5000:1, 10,000:1, 50,000:1, or 100,000:1, or within a range thathas any of these values as the upper or lower bounds.

When the cyclic olefin comprises a cyclic olefinic hydrocarbon and acyclic alkenol, the molar ratio of the two compounds will vary dependingon the desired products. For example, the molar ratio of the cyclicolefinic hydrocarbon to the cyclic alkenol may be 100:1, 50:1, 25:1,10:1, 5:1, 2:1, 1:1, 1:2, 1:5, 1:10, 1:25, 1:50, or 1:100, or within arange that has any of these values as the upper or lower bounds.

II. Second Embodiment Further Reactions

In a second embodiment, the invention provides a method formanufacturing a wax. The method involves ring-opening, ring insertionmetathesis of at least one olefinic substrate and at least one cyclicolefin as the cross metathesis partner. As with the first embodiment,the olefinic substrate is selected from (i) an unsaturated fatty acid,(ii) an unsaturated fatty alcohol, (iii) an esterification product of anunsaturated fatty acid with an alcohol, and (iv) an esterificationproduct of a saturated fatty acid with an unsaturated alcohol. Thereaction is carried out catalytically, generally in the presence of aruthenium alkylidene metathesis catalyst, by contacting the at least oneolefinic substrate with the cross metathesis partner, i.e., the at leastone cyclic olefin, in the presence of the metathesis catalyst underreaction conditions effective to allow ring insertion cross metathesiswhereby the cyclic olefin is simultaneously opened and inserted into theolefinic substrate to provide an olefinic product. This embodimentfurther comprises partially or completely hydrogenating the olefinicproduct. The disclosure, supra, with respect to the components andmethods of the first embodiment also applies to the second embodiment.

Methods suitable for carrying out the partial or complete hydrogenationof the olefinic product are known in the art, and any appropriatehydrogenation method may be employed. Typically, such methods involveplacing the olefinic product in a suitable container, introducing ahydrogenation catalyst, if necessary, and introducing a hydrogen source.Suitable methods for hydrogenation may be found, for example, in Smithet al. March's Advanced Organic Chemistry, 5th Edition (Wiley: New York,2001).

The hydrogenation of the olefinic product of the reaction may be carriedout with or without isolation of the olefinic products from the ringinsertion cross metathesis reaction. It will be appreciated that thehydrogenation reaction will, in some instances, be affected by thepurity of the reaction mixture and the presence of impurities from thering insertion cross metathesis reaction. In such cases, the yield ofthe hydrogenated olefinic products can be maximized by isolating andpurifying the olefinic products before hydrogenation is performed.

Any catalyst suitable for hydrogenating the olefinic products may beemployed, and appropriate catalysts may also be found, for example, inSmith et al. March's Advanced Organic Chemistry, 5th Edition (Wiley: NewYork, 2001). In one example, the ruthenium alkylidene metathesiscatalysts that is used for the ring insertion cross metathesis reactionmay also be employed as the hydrogenation catalyst. In this embodiment,it is not necessary to add a further hydrogenation catalyst to thereaction mixture in order to perform the hydrogenation.

III. Third Embodiment Process with the Grubbs-Hoveyda Catalyst

In a third embodiment, the invention provides an olefin cross-metathesismethod in which the method involves ring-opening, ring insertionmetathesis of at least one olefinic substrate and at least one cyclicolefin as the cross metathesis partner. The reaction is carried outcatalytically, generally in the presence of a ruthenium alkylidenemetathesis catalyst. In this embodiment, the reaction is carried out bycontacting the at least one olefinic substrate with the cross metathesispartner, i.e., the at least one cyclic olefin, in the presence of themetathesis catalyst under reaction conditions effective to allow ringinsertion cross metathesis whereby the cyclic olefin is simultaneouslyopened and inserted into the olefinic substrate. Furthermore, in thisembodiment, the catalyst is a Grubbs-Hoveyda complex, as described indetail for the first embodiment, supra.

IV. Fourth Embodiment Reaction System

In a fourth embodiment, the invention provides a reaction system. As anexample, a reaction system is provided for carrying out a catalyticring-opening cross-metathesis reaction comprising at least one olefinicsubstrate, at least one cyclic olefin, and a ruthenium alkylidene olefinmetathesis catalyst. The at least one olefinic substrate is selectedfrom (i) an unsaturated fatty acid, (ii) an unsaturated fatty alcohol,(iii) an esterification product of an unsaturated fatty acid with analcohol, and (iv) an esterification product of a saturated fatty acidwith an unsaturated alcohol. The reaction system may further comprise asolvent.

In a second example of this embodiment, the reaction mixture comprisesat least one olefinic substrate, an unsubstituted cyclic olefin, acyclic alkenol, and a ruthenium alkylidene metathesis catalyst.

In another example, a reaction system is provided for manufacturing awax. The reaction system comprises at least one olefinic substrate, atleast one cyclic olefin, and a ruthenium alkylidene olefin metathesiscatalyst. The at least one olefinic substrate is selected from: (i) anunsaturated fatty acid; (ii) an unsaturated fatty alcohol; (iii) anesterification product of an unsaturated fatty acid with an alcohol; and(iv) an esterification product of a saturated fatty acid with anunsaturated alcohol.

Detailed descriptions of each of these reaction components can be foundin the disclosure of the first embodiment, supra.

V. Fifth Embodiment Products

In a fifth embodiment, the invention provides compounds andcompositions. For example, the invention provides compounds that areprepared using any of the reactions and/or reaction systems disclosedherein. Such compounds may be monomers, dimmers, trimers, oligomers,higher order species, or mixtures thereof. Such compounds may bechain-extended olefinic substrates such as glycerides. Examples ofchain-extended glycerides include chain-extended monoglycerides,chain-extended diglycerides, chain-extended triglycerides, higher orderchain-extended glycerides, and combinations thereof.

VI. Sixth Embodiment Kit of Parts

In a fifth embodiment, the invention provides a kit of parts. As anexample, a kit of parts is provided for carrying out a catalyticring-opening cross metathesis reaction. The kit of parts comprises atleast one olefinic substrate and a ruthenium alkylidene olefinmetathesis catalyst. The catalyst is present in an amount that is lessthan 1000 ppm relative to the olefinic substrate, and the at least oneolefinic substrate is selected from (i) an unsaturated fatty acid, (ii)an unsaturated fatty alcohol, (iii) an esterification product of anunsaturated fatty acid with an alcohol, and (iv) an esterificationproduct of a saturated fatty acid with an unsaturated alcohol. The kitof parts further comprises: (a) at least one cyclic olefin; or (b)instructions for adding a cyclic olefin to the at least one olefinicsubstrate. The at least one olefinic substrate, the ruthenium alkylideneolefin metathesis catalyst, and the at least one cyclic olefin (whenpresent) may be combined in a mixture or may be contained separately.

In a preferred embodiment of the kit of parts for carrying out acatalytic ring-opening cross metathesis reaction, the kit comprises atleast one cyclic olefin. The at least one olefinic substrate is combinedin a mixture with the at least one olefinic substrate, and this mixtureis contained separately from the ruthenium alkylidene olefin metathesiscatalyst.

In another example, a kit of parts is provided for manufacturing a wax.The kit of parts comprises at least one olefinic substrate and aruthenium alkylidene olefin metathesis catalyst. The catalyst is presentin an amount that is less than 1000 ppm relative to the olefinicsubstrate, and the at least one olefinic substrate is selected from (i)an unsaturated fatty acid, (ii) an unsaturated fatty alcohol, (iii) anesterification product of an unsaturated fatty acid with an alcohol, and(iv) an esterification product of a saturated fatty acid with anunsaturated alcohol. The kit of parts further comprises: (a) at leastone cyclic olefin; or (b) instructions for adding a cyclic olefin to theat least one olefinic substrate. The kit of parts further comprisesinstructions for hydrogenating metathesis products, and the kit mayfurther comprises materials useful for hydrogenating metathesisproducts.

In a preferred embodiment of the kit of parts for manufacturing a wax,the kit comprises at least one cyclic olefin. The at least one olefinicsubstrate is combined in a mixture with the at least one olefinicsubstrate, and this mixture is contained separately from the rutheniumalkylidene olefin metathesis catalyst.

Detailed descriptions of each of these reaction components can be foundin the disclosure of the first embodiment, supra.

Utility

The metathesis products from the methods disclosed herein are useful,for example, as binders in urethane foams, latex paints, printing inksand as high melting point waxes. As described hereinabove, the doublebonds may be partially or completely hydrogenated to produce waxes ofvarying melting points.

It is to be understood that while the invention has been described inconjunction with specific embodiments thereof, that the descriptionabove as well as the examples that follow are intended to illustrate andnot limit the scope of the invention. Other aspects, advantages, andmodifications within the scope of the invention will be apparent tothose skilled in the art to which the invention pertains.

EXPERIMENTAL

In the following examples, efforts have been made to ensure accuracywith respect to numbers used (e.g., amounts, temperature, etc.) but someexperimental error and deviation should be accounted for. Unlessindicated otherwise, temperature is in degrees C. and pressure is at ornear atmospheric.

EXAMPLES

General Metathesis Procedure for Production and Analysis of MetathesizedOil Polyol and Chain-Extended Samples. To a clean and dry 2-Lround-bottomed flask is added approximately 500 g of seed oil (e.g.,refined bleached deodorized soybean oil (RBDSBO), Castor Oil, volatilelights removed metathesized soybean oil (RMSBO), soybean oil fatty acidmethyl esters (Soy FAME), caster oil fatty acid methyl esters (CastorFAME), etc.) containing a PTFE lined stir bar. To the oil is added oneor more reagents (e.g., cyclooctene, 5-hydroxymethyl-2-norbornene,etc.), in mole ratio ranging from 0.1 mol % to 200 mol %. The mixture isdegassed with Argon for one hour with stirring. After degassing, anappropriate mass of metathesis catalyst such as C827 (1) (i.e.,[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro[3-methyl-2-buteneylidene]-tricyclohexylphosphine)ruthenium) is added as a solid to the reaction mixture at roomtemperature, at which point the vessel is blanketed with Argon, sealed,and placed in a 70° C. oil bath. When the temperature of the bathreaches 70° C. again, the time is recorded and the reaction is allowedto stir for two hours. The catalyst may be removed or the reactionmixture can be used without further purification. After two hours, analiquot is taken from the reaction and added to about 1 mL of 1%NaOMe/MeOH solution in a vial, which is placed in a heating block at 70°C. for 30 min in order to transesterify the triglyceride products intomethyl esters. After 30 min, the solution is allowed to cool. The cooledsolution is hydrolyzed, and then the organics extracted using arelatively non-polar solvent (e.g., hexanes, ether, etc.). The organiclayer is analyzed by GC; unless otherwise noted, conversion iscalculated and reported based on the disappearance of the startingmaterial. It is noted whether all or some of the reaction solidified,and, in some cases, a viscosity measurement is taken.

Catalyst Removal Procedure: A 1.0 M solution oftris(hydroxymethyl)phosphine (THMP) in isopropanol (IPA) (25 mol equivof THMP per mole of metathesis catalyst) was added to the metathesizedoil and the mixture was heated at 70° C. for 6 hours (under argon) (R.L. Pederson; I. M. Fellows; T. A. Ung; H. Ishihara; S. P Hajela Adv.Syn. Cat. 2002, 344, 728). Hexanes was added if needed to form a secondphase when the mixture was washed 3 times with water. The organic phasewas dried with anhydrous Na₂SO₄, filtered and analyzed by GC analysis.

Alternative Catalyst Removal Procedure: A 1.0 M solution oftris(hydroxymethyl)phosphine (THMP) in IPA (25 mol equiv of THMP permole of metathesis catalyst) was added to the metathesized oil and themixture was heated at 70° C. for 6 hours (under argon) (R. L. Pederson;I. M. Fellows; T. A. Ung; H. Ishihara; S. P Hajela Adv. Syn. Cat. 2002,344, 728). IPA was then removed via rotary evaporator (part of volatileterminal olefins were also removed), 5 wt % of bleaching clay (Pure FlowB80 CG) to product was added to the crude reaction mixture and stirredovernight under argon at 70° C. The crude product mixture containing theclay was subsequently filtered through a packed bed of sand (10 g),celite (5 g), bleaching clay (12.5 g), and sand (10 g). The filtered oilwas analyzed by GC analysis.

General Procedure for the Transesterification of Metathesized Seed oils:To a glass 3-necked round bottom flask with a magnetic stirrer,condenser, temperature probe, and a gas adapter was charged with crudemetathesized SBO product (˜1 L) and 1% w/w NaOMe in MeOH (˜3 L). Theresulting light yellow heterogeneous mixture was stirred at 60° C. for 1hr. Towards the end of the hour, the mixture turned a homogeneous orangecolor. Esterified products were transferred into the separatory funneland extracted with 2.0 L DI—H₂O. The aqueous layer was then extractedwith 2×2.0 L Et₂O. The combined organic extracts were dried over 300 g.of anhydrous Na₂SO₄ for 20 hours. The solution of esterified productswas filtered and the filtrate was stripped of solvent via rotaryevaporator.

Viscosity methods: All readings were taken at 30° C. using a BrookfieldDigital Viscometer Model DV-II and S62 spindle. RPM values weredependent on individual viscosity of the material.

GC Analysis Conditions and methods: The products were analyzed using anAgilent 6890 gas chromatography (GC) instrument with a flame ionizationdetector (FID). The following conditions and equipment were used:

Column: Rtx-5, 30 m × 0.25 mm (ID) × 0.25 μm film thickness.Manufacturer: Restek GC and column Injector temperature: 250° C.conditions: Detector temperature: 280° C. Oven temperature: Startingtemperature: 100° C., hold time: 1 minute. Ramp rate 10° C./min to 250°C., hold time: 12 minutes. Carrier gas: Helium Mean gas velocity: 31.3 ±3.5% cm/sec (calculated) Split ratio: ~50:1The products were characterized by comparing peaks with known standards,in conjunction with supporting data from mass spectrum analysis(GCMS-Agilent 5973N). GCMS analysis was accomplished with a secondRtx-5, 30 m×0.25 mm (ID)×0.25 μm film thickness GC column, using thesame method as above.

Materials and methods: Seed oils were obtained from Cargill. In theExamples that follow, all reactions were carried out using the specifiedcatalyst loading as moles of catalyst to moles of seed oils. Catalystsare referenced using their molecular weights, as described hereinabove.In the Examples, the abbreviation RMSBO refers to Removed-LightsMetathesized Soy Bean Oil, which is self-metathesized RBSBO in which thelight oils and olefins have been removed by flash distillation.Self-metathesis of seed oils is described in WO 2006/076364. Referenceis also made to various cyclic olefins using the followingabbreviations:

Example 1

Various compounds were analyzed using the GCMS methods described above.Data are provided in table 1.

TABLE 1 Common Products from the Cross Metathesis of Seed Oils. CompoundRet Time (min) Compound Abbreviation 1.300 E-2-Octene 2C₈ 1.596 3-Nonene3C₉ 2.039 1-Decene 1C₁₀ 2.907 E-2-Undecene E-2C₁₁ 3.001 Z-2-UndeceneZ-2C₁₁ 3.836 3-Dodecenes 3C₁₂ 5.298 Methyl 9-Decenoate 9C₁₀O₂Me 7.419Pentadecadienes nC₁₅ 7.816 Methyl E-9-Dodecenoate E-9C₁₂O₂Me 7.894Methyl Z-9-Dodecenoate Z-9C₁₂O₂Me 10.939 9-Octadecene 9C₁₈ 11.290 Methyl9-12 tetradecadienoate 9,12C₁₄O₂Me 12.523 Methyl palmitate C₁₆O₂Me14.306 Methyl linoleates 9,12C₁₈O₂Me 14.363 Methyl oleates 9C₁₈O₂Me14.537 Methyl stearate C₁₈O₂Me 17.138 Methyl 9,21-Henicosadienaote9,12C₁₈O₂Me 17.586 1,18 Dimethyl ester of 9-Ocadecene 9,12C₁₈O₂Me 22.236Methyl 9,12,15-docosatrienoate 9,12,15C₂₁O₂Me

Example 2

A model study was undertaken to prove that ROCM reactions produced thedesired higher molecular weight products. This study examined reactionof simple acyclic olefins with cyclooctene to determine and characterizethe ROCM products formed.

In a ROCM reaction, a cyclic alkene undergoes the ring-openingmetathesis reaction to produce the mixture of ring-opened products. Onceopened, it will cross metathesize with an acyclic alkene such as SBO orSBO FAME to yield a new high molecular weight product. Hence the ROCMproduct should be a mixture of cyclic alkene inserted-products. Tounderstand the ROCM product distributions, several ROCM reactions havebeen studied under different ratios of cyclic alkene to acyclic alkene.

GC and GC-MS Results of ROCM Products:

Conversion in each reaction was determined by measuring thedisappearance of the starting internal alkene when compared to dodecaneas an internal standard. The GC and GC-MS analyses were determined andROCM products were characterized up to n=3 cyclic olefin insertedproducts. When n was >3, these products were above our detection limitof our instruments. The ratio of higher than 3-ring inserted product wasfound to increase with higher loading of cycloalkene.

GC and GC-MS Analysis of ROCM Products:

Well defined olefins were run under ROCM conditions with cyclic olefinsto yield higher molecular weight products. GC and GC-MS analysis ofthese products identified up to 3 cyclic ring inserted compounds. Thering inserted products were characterized by GC and their molecularweights were determined by GC-MS analysis. The detection limit of our GCand GC-MS was n=3; when n>3 higher molecular weight products did notelute as sharp interpretable peaks. The n>3 value represents highmolecular products that were not identified by GC or GC-MS, this valuewas calculated by 100% minus percent unreacted starting minus n=1, n=2and n=3 percentages. The data below demonstrates the productdistributions for the ratios of starting materials indicated.

I. GC Results of ROCM of 9-Octadecene (9C18) and Cyclooctene andCyclododecene.

% insertion product m % SM^(a) n = 1 n = 2 n = 3 n>3 0.5 42 14 2 <1 42 149 19 8 4 20 2 31 20 9 <1 40 3 23 17 11 1 48 5 15 11 7 1 66 10 14 6 4 <177 ^(a)% SM represents the amount of unreacted starting acyclic olefinpresent at the end of the reaction.

% insertion product m % SM n = 1 n = 2 n = 3 n>3 1 47 13 7 <1 33

FIG. 1 depicts a typical GC-MS chromatogram of ROCM (n=1) products. Thepeaks at 20.10 min to 20.40 min are cis and trans-isomers of the n=1ROCM product. The molecular weights of these peaks were determined to be362, which corresponds to the product.

FIG. 2 depicts the MALD-TOF study of 9C18 and COE ROCM reactions. Thereaction was run in a potassium salt matrix which explains why themolecular weights are 56 units higher than expected. The data clearlyshows that each 110 repeat unit (when n=1 to 7) corresponds to anotherinsertion of COE. With this technique, repeat units of up to n=7 COEinserted units have been identified. The GC-MS and MALDI-TOF dataclearly demonstrated that the COE units are being inserted into the9-octadecene to produce the desired ROCM high molecular weight products.

II. GC Results of ROCM of 1,18-Dimethyl esters of 9-Octadecene(9C18-diester) with Cyclooctene, Cyclododecene or Norbornene EthyleneGlycol Ester (NBE).

% insertion product m % SM n = 1 n = 2 n = 3 n>3 0.5 65 16 2 <1 18 1 6815 4 <1 13 2 32 16 5 <1 48 3 25 31 7 <1 37 5 17 10 3 <1 70 10 10 5 1 <184

% insertion product m % SM n = 1 n = 2 n = 3 n>3 1 42 6 13 <1 38

% insertion product m % SM n = 1 n = 2 n = 3 n>3 1 70 3 <3 <3 27

III. GC Results of ROCM of Methyl Oleate (MO) with Cyclooctene,Cyclododecene or Norbornene Ethylene Glycol Ester (NBE).

% insertion product m % SM n = 1(A,B,C) n = 2(A,B,C) n = 3 n>3 0.5 6415(5,8,2) 2(1,1,0) 1 18 1 46 14(4,7,3) 6(1,3,2) 2 32 2 31 18(5,9,4)9(3,5,1) 1 40 3 26 18(5,9,4) 9(3,5,1) 2 46 5 22  9(2,5,2) 3(1,2,1) 1 6510 17  7(2,4,1) 2(1,1,0) <1 74

% insertion product m % SM n = 1 n = 2 n = 3 n>3 1 46 14 4 <1 37

% insertion product m % SM n = 1 n = 2 n = 3 n>3 1 46 4 <1 <1 50

IV. GC Results of ROCM of Castor Oil Fatty Acid Methyl Ester (CastorFame) with Cyclooctene

% insertion product m % SM n = 1(A,B,C) n = 2(A,B,C) n = 3 n>3 0.5 5814(4,7,3) 2(1,1,0) <1 26 1 52 19(4,10,5) 7(1,4,2) <1 22 2 31 16(4,8,4)6(2,4,0) <1 47 3 25 14(4,7,3) 7(2,4,1) <1 54 5 16 10(3,5,2) 5(1,3,1) <170 10 13  7(2,4,1) 3(1,1,1) 1 77

These results demonstrated that the cyclic olefins are inserted into theseed oils, up to our level of detection by GC and GC-MS. Moreover, theseresults indicated that the reactions using higher ratios of cyclicolefins to acyclic alkene produced higher molecular weight products asdetermined by the lower ratio of unreacted starting materials, n=1, n=2and n=3 detectable products, thereby it is possible to control themolecular weight of product. To further prove ROCM products, MALDI-TOFanalysis was done on sample JP.125.193B. This data clearly showsinsertion of the cyclooctene up to n=7 increasing repeat units.

Example 3

Using the General Metathesis procedure described above, various FAMEswere reacted with various cyclic olefins using the ruthenium alkylidenemetathesis catalyst C827. The results are given in Table 2.

TABLE 2 Ring Opening Cross Metathesis Products Cyclic FAME Olefin C827Conv.¹ Cyclic Reaction # FAME Cyclic Olefin mol % (ppm) (Y/N) Conv.¹(Y/N) JP.125.085 MO No 200 Y NA JP.125.051M ML No 200 Y NA JP.125.184GNone NBM None NA NA JP.125.184H None NBE None NA NA JP.125.084K NoneCydecanol None NA NA JP.125.084E None NBM 200 Solid, no GC JP.125.084FNone NBE 200 Solid, no GC CWL81-143 None Cydecanol 200 N JP.125.084A MONBM 50 None NA NA JP.125.084B MO NBE 50 None NA NA JP.125.084I MOCydecanol 50 None NA NA JP.125.084C ML NBM 50 None NA NA JP.125.084D MLNBE 50 None NA NA JP.125.084J ML Cydecanol 50 None NA NA JP.125.051A MONBM 50 200 Y Y JP.125.051B MO NBM 20 200 Y Y JP.125.051C MO NBM 10 200 YY JP.125.051D MO NBE 50 200 Y Y JP.125.051E MO NBE 20 200 Y YJP.125.051F MO NBE 10 200 Y Y CWL81- MO Cydecanol 50 200-100 Y N 143AJP.125.051G ML NBM 50 200 Y Y JP.125.051H ML NBM 20 200 Y Y JP.125.051IML NBM 10 200 Y Y JP.125.051H ML NBE 50 200 Y Y JP.125.051K ML NBE 20200 Y Y JP.125.051L ML NBE 10 200 Y Y JP.125.066 ML Cydecanol 50 200 Y N¹Conv.: refers to whether metathesis occurred with each individualmaterial; not a numerical value.

The data in Table 2 demonstrate that various FAMEs and cyclic olefinsare good substrates for metathesis. However, cyclecanol was a poorsubstrate for metathesis under the standard reaction conditions (likelydue to low ring strain) but did not negatively impact metathesis ofother olefins with which it was mixed.

Example 4

Ring opening cross metathesis was carried out according to the GeneralMetathesis Procedure using SBO and either NBM or NBE. The results areprovided in Table 3. Conversion percent refers to the amount of newmetathesis products formed as calculated by 100% minus the percent ofunreacted starting materials.

TABLE 3 Ring insertion cross metathesis of SBO with NBM or NBE CyclicSeed Oil/ Cyclic olefin C827 Conv. Product Viscosity Reaction # Batch #Olefin mol % (ppm) (%) a Solid^(a) (cP)^(b) AV078-114C SBO/F5L19 — 0 5068 N 189 JP.105.128 SBO/F5L19 NBM 5 50 67 JP.105.142 SBO/F5L19 NBM 20 5054 198 CWL81-108 SBO/F5L19 NBE 5 50 69 192 CWL81-109A SBO/F5L19 NBE 5100 70 132 CWL81-109B SBO/F5L19 NBE 10 50 69 186 CWL81-109C SBO/F5L19NBE 10 100 69 240 CWL81-110A SBO/F5L19 NBE 20 50 67 230 CWL81-110BSBO/F5L19 NBE 20 100 69 276 JP.105.171 SBO/F5L19 NBE 35 100 67 YJP.105.172 SBO/F5L19 NBE 50 100 68 Y 3780 JP.105.184 SBO/F5L19 NBE 100100 62 Y JP.105.160 SBO/F5L19 NBE 200 400 70 Y ^(a)Metathesis productwas a solid or precipitated. ^(b)Viscosities were measured at 30~40 C.using S62 spindle with Brookfield DV-II+ viscometer

The data demonstrates that NBM and NBE are substrates for ROCMreactions. The metathesis of neat SBO will reach 68% conversion atequilibrium. ROCM products are shown by the increased viscosity readingof the ROCM products compared to neat SBO.

Example 5

Ring opening cross metathesis was carried out according to the GeneralMetathesis Procedure using SBO/F5L19 as olefinic substrate and Cydol ascyclic olefin. The results are provided in Table 4.

TABLE 4 Ring opening cross metathesis of SBO and Cydol Cyclic OlefinViscosity Reaction # mol % C827 (ppm) Conv. (%) (cP) AV078-114C 0 50 68189 JP.105.122 5 50 65 173 JP.105.124 5 100 68 179 JP.105.123 10 50 64JP.105.125 10 100 67 160 JP.105.126 20 50 63 179 JP.105.127 20 100 68170 JP.105.173 35 100 63 JP.105.174 50 100 53 JP.105.161 100 200 68JP.105.162 200 200 56 Cydol is a poor substrate for metathesis ROCMapplications but it does not have an inhibitory effect on the metathesiscatalyst.

Cydol is a poor substrate for metathesis ROCM applications but it doesnot have an inhibitory effect on the metathesis catalyst.

Example 6

Ring opening cross metathesis was carried out according to the GeneralMetathesis Procedure using SBO/F5L19 as olefinic substrate and with HNB,NBM and Cydol as cyclic olefins. The results are provided in Table 5.

TABLE 5 Ring insertion cross metathesis of SBO and HNB Cyclic OlefinC827 Conv. Reaction # Cyclic Olefin mol % (ppm) (%) CWL81-124A HNB/NBM10/0.2 50 69 CWL81-124B HNB/NBM 10/1.0 50 69 CWL81-126A HNB/NBE 10/1.050 70 CWL81-126B HNB/NBE 20/1.0 50 70 CWL81-127A HNB/Cydol 10/1.0 50 69CWL81-127B HNB/Cydol 20/1.0 50 68 HNB, NBE, NBM and Cydol do not have aninhibitory effect on the metathesis catalyst or the metathesis of SBO.

HNB, NBE, NBM and Cydol do not have an inhibitory effect on themetathesis catalyst or the metathesis of SBO.

Example 7

Ring opening cross metathesis was carried out according to the GeneralMetathesis Procedure using SBO as olefinic substrate and BNB, NBM, NBEand Cydol as cyclic olefins. The results are provided in Table 6.

TABLE 6 Ring insertion cross metathesis of SBO and BNB Cyclic Seed Oil/Olefin C827 Conv. Reaction # Batch # Cyclic Olefin mol % (ppm) (%)JP.125.064 SBO/F6C13 BNB/NBM 100/20 200 67 JP.125.065 SBO/F6C13 BNB/NBM200/20 300 66 JP.125.013 SBO/F5J26 BNB/NBE  50/10 100 69 JP.125.014SBO/F5J26 BNB/NBE 100/10 100 66 JP.125.015 SBO/F5J26 BNB/NBE 100/20 20068 JP.125.016 SBO/F5J26 BNB/NBE 200/20 300 67 JP.125.026 SBO/F5J26BNB/Cydol  50/10 100 69 JP.125.027 SBO/F5J26 BNB/Cydol 100/10 100 68JP.125.028 SBO/F5J26 BNB/Cydol 100/20 200 69 JP.125.029 SBO/F5J26BNB/Cydol 200/20 300 68

BNB, NBM, NBE and Cydol do not have an inhibitory effect on themetathesis catalyst.

Example 8

Ring opening cross metathesis was carried out according to the GeneralMetathesis Procedure using SBO as olefinic substrate and COE, NBM, NBEand Cydol as the cyclic olefins. The results are provided in Table 7.

TABLE 7 Ring insertion cross metathesis of SBO and COE Cyclic Seed Oil/Olefin C827 Conv. Viscosity Reaction # Batch # Cyclic Olefin mol % (ppm)(%) (cP) JP.105.155 SBO/F5L19 COE/NBM 10/1.0 50 64 JP.125.052 SBO/F6C13COE/NBM 50/10  100 70 JP.125.054 SBO/F6C13 COE/NBM 100/20   200 71JP.125.055 SBO/F6C13 COE/NBM 200/20   300 73 256 CWL81-129A SBO/F5L19COE/NBE 10/1.0 50 70 CWL81-129B SBO/F5L19 COE/NBE 20/1.0 50 70CWL81-136B SBO/F5L19 COE/NBE 50/1.0 100 72 179 JP.105.208 SBO/F5J26COE/NBE 50/10  100 68 CWL81-136A SBO/F5L19 COE/NBE 100/10   100 71JP.125.017 SBO/F5J26 COE/NBE 100/20   100 70 JP.125.018 SBO/F5J26COE/NBE 200/20   200 76 468 CWL81-128A SBO/F5L19 COE/Cydol 10/1.0 50 69CWL81-128B SBO/F5L19 COE/Cydol 20/1.0 50 69 CWL81-135B SBO/F5L19COE/Cydol 50/1.0 100 72 CWL81-137B SBO/F5L19 COE/Cydol 50/10  100 71CWL81-135A SBO/F5L19 COE/Cydol 100/10   100 71 CWL81-137A SBO/F5L19COE/Cydol 100/20   100 71 JP.105.198 SBO/F5L19 COE/Cydol 200/20   100 72

COE, NBM, and NBE readily participate in ROCM reactions as indicated bytheir increased viscosity measurements and do not have an inhibitoryeffect on the metathesis catalyst.

Example 9

Ring insertion cross metathesis was carried out according to the GeneralMetathesis Procedure using SBO as olefinic substrate and CDDE, NBE andCydol as the cyclic olefins. The results are provided in Table 8.

TABLE 8 Ring opening cross metathesis of SBO and CDDE Cyclic Seed Oil/Olefin C827 Conv. Viscosity Reaction # Batch # Cyclic Olefin mol % (ppm)(%) (cP)a JP.125.025 SBO/F5J26 CDDE/NBE  50/10 100 67 JP.125.019SBO/F5J26 CDDE/NBE 100/20 100 68 JP.125.020 SBO/F5J26 CDDE/NBE 200/20200 74 JP.105.193 SBO/F5L19 CDDE/Cydol  50/10 100 68 JP.105.194SBO/F5L19 CDDE/Cydol 100/10 200 68 JP.105.195 SBO/F5L19 CDDE/Cydol100/20 200 73 JP.105.197 SBO/F5L19 CDDE/Cydol 200/20 200 75 800

CDDE readily participate in ROCM reactions as indicated by its increasedviscosity measurement and does not have an inhibitory effect on themetathesis catalyst.

Example 10

Ring opening cross metathesis was carried out according to the GeneralMetathesis Procedure using SBO as olefinic substrate and DCPD, NBM, NBEand Cydol as cyclic olefins. The results are provided in Table 9.

TABLE 9 Ring insertion cross metathesis of SBO and DCPD Cyclic Seed Oil/Olefin C827 Conv. Reaction # Batch # Cyclic Olefin mol % (ppm) (%)JP.105.150 SBO/F5L19 DCPD/NBM   10/1.0 50 63 JP.105.151 SBO/F5L19DCPD/NBM   10/1.0 100 69 JP.125.056 SBO/F6C13 DCPD/NBM  50/10 100 65JP.125.057 SBO/F6C13 DCPD/NBM 100/10 100 68 JP.125.058 SBO/F6C13DCPD/NBM 100/20 200 67 JP.125.059 SBO/F6C13 DCPD/NBM 200/20 300 67JP.105.180 SBO/F5L19 DCPD/NBE   10/1.0 100 68 JP.105.181 SBO/F5L19DCPD/NBE   20/1.0 100 68 JP.125.001 SBO/F5J26 DCPD/NBE  50/10 100 68JP.125.002 SBO/F5J26 DCPD/NBE 100/10 200 68 JP.125.003 SBO/F5J26DCPD/NBE 100/20 200 67 JP.125.004 SBO/F5J26 DCPD/NBE 200/20 300 68JP.105.177 SBO/F5L19 DCPD/Cydol   10/1.0 100 68 JP.105.178 SBO/F5L19DCPD/Cydol   20/1.0 100 67 JP.105.188 SBO/F5L19 DCPD/Cydol 50/5 100 67JP.105.189 SBO/F5L19 DCPD/Cydol  50/10 100 69 JP.105.191 SBO/F5L19DCPD/Cydol 100/10 200 71 JP.105.192 SBO/F5L19 DCPD/Cydol 100/20 200 69JP.105.207 SBO/F5J26 DCPD/Cydol 200/20 400 73

DCPD, NBE, NBM and Cydol do not have an inhibitory effect on themetathesis catalyst.

Example 11

Ring insertion cross metathesis was carried out according to the GeneralMetathesis Procedure using SBO/F5J26 as olefinic substrate and CDTE, NBEand Cydol as olefinic substrates. The results are provided in Table 10.

TABLE 10 Ring insertion cross metathesis of SBO and CDTE Cyclic OlefinC827 Conv. Reaction # Cyclic Olefin mol % (ppm) (%) JP.125.007 CDTE/NBE100/20 200 74 JP.125.008 CDTE/NBE 200/20 400 75 JP.125.009 CDTE/Cydol 50/10 100 71 JP.125.010 CDTE/Cydol 100/10 200 74 JP.125.011 CDTE/Cydol100/20 200 74 JP.125.012 CDTE/Cydol 200/20 300 75

CDTE, NBE and Cydol do not have an inhibitory effect on the metathesiscatalyst.

Example 12

Ring opening cross metathesis was carried out according to the GeneralMetathesis Procedure using lights removed metathesized soybean oil(RMSBO) as olefinic substrate and various cyclic olefins. The resultsare provided in Table 11.

RMSBO is produced by metathesizing SBO to 68% conversion, then removingthe lights under high vacuum while heating to 200° C. This processremoves ˜8 wt % of light hydrocarbons from the reaction.

TABLE 11 Ring opening cross metathesis of RMSBO and Cyclic Olefins Ratioof Cyclic Olefin C827 Conv. Product 9C₁₅ ester to Reaction # CyclicOlefin mol % (ppm) (%) a Solid^(a) palmitate^(b) RLP 66-084 none 0 50 68no 1.40 CWL81-133 COE/NBM   10/1.0 50 67 JP.125.068 COE/NBM  50/10 10066 0.72 JP.125.069 COE/NBM 100/10 100 71 Y (clear elastic) 0.44JP.125.070 COE/NBM 100/20 200 73 0.40 JP.125.071 COE/NBM 200/20 300 73 Y(clear elastic) 0.38 CWL81-130 COE/NBE   10/1.0 50 66 JP.125.072 COE/NBE 50/10 100 71 0.57 JP.125.087 COE/NBE 100/5  100 72 0.42 JP.125.073^(c)COE/NBE 100/10 100 74 0.43 JP.125.074 COE/NBE 100/20 200 72 0.39JP.125.075 COE/NBE 200/20 300 73 0.29 JP.105.200 COE/Cydol 100/5  200 70Y (elastic) 0.47 JP.105.201 COE/Cydol  50/10 200 67 0.87 JP.105.202COE/Cydol 100/20 200 70 Y (elastic) 0.62 JP.105.203 COE/Cydol 200/20 20072 Y (elastic) 0.44 JP.125.129 CDDE/NBE  50/10 100 70 0.95 JP.125.130CDDE/NBE 100/10 100 69 0.89 JP.125.131 CDDE/NBE 100/20 200 72 0.70JP.125.132 CDDE/NBE 200/20 400 76 0.41 JP.125.088 DCPD/NBE 100/5  100 721.39 JP.125.080 DCPD/NBE  50/10 100  92? 1.23 JP.125.081 DCPD/NBE 100/10200 69 1.41 JP.125.082 DCPD/NBE 100/20 300 71 0.97 JP.125.083 DCPD/NBE200/20 400 69 Y (white wax) 1.27 JP.125.089 DCPD/Cydol 100/5  200 691.02 JP.125.076 DCPD/Cydol  50/10 100  85? 0.53 JP.125.077 DCPD/Cydol100/10 200 69 1.36 JP.125.078 DCPD/Cydol 100/20 300 68 1.21 JP.125.079DCPD/Cydol 200/20 400 70 Y (white wax) 1.16 ^(a)Metathesis product was asolid or precipitated. ^(b)Ratio of 9C15ester to palmitate usespalmitate as an internal standard to determine the conversion of SBO toROCM products. The 9C15 ester is consistently produced in SBO metathesisreactions. Plamitate is inert to metathesis and is easy intergrate byGC, therefore it is an ideal internal standard in these SBO metathesisreactions. ^(c)Viscosity of sample was 14300 cP

COE, NBM, NBE, Cydol and DCPD do not have an inhibitory effect on themetathesis catalyst. The decrease in the 9C15 ester to palmitate ratioindicates that the cyclic olefins are ring opening cross metathesizingwith SBO to form new products.

Example 13

Ring opening cross metathesis was carried out according to the GeneralMetathesis Procedure using castor oil as olefinic substrate and HNB,BNB, COE, DCPD and CDDE as cyclic olefins. The results are provided inTable 12.

TABLE 12 Ring opening cross metathesis of Caster Oil and Cyclic OlefinsCyclic Cyclic Olefin C827 Conv. Reaction # Olefin mol % (ppm) (%)JP.105.139 HNB 20 200 58 JP.105.140 HNB 20 400 57 JP.125.037 BNB 50 20058 JP.125.038 BNB 100 200 59 JP.125.039 BNB 200 400 58 JP.105.133 COE 5100 46 JP.105.134 COE 5 200 55 JP.105.136 COE 10 100 46 JP.105.135 COE10 200 56 CWL81-115A COE 20 100 42 CWL81-115B COE 20 200 58 CWL81-115CCOE 20 400 59 JP.125.035 COE 50 200 62 JP.105.163 COE 100 200 62JP.105.164 COE 200 400 75 JP.105.144 DCPD 10 200 61 JP.105.145 DCPD 20400 59 JP.125.032 DCPD 50 200 56 JP.125.033 DCPD 100 200 54 JP.125.034DCPD 200 400 43 CWL81-117C CDDE 10 200 53 CWL81-117A CDDE 20 200 56CWL81-117B CDDE 20 400 59 CWL81-142 none N/A 200 58

HNB, BNB, COE, DCPD and CDDE do not have an inhibitory effect on themetathesis catalyst.

Example 14

Ring opening cross metathesis was carried out according to the GeneralMetathesis Procedure using SBO/F5J26 as olefinic substrate and COE,CDDE, DCPD, CDTE and ENB as cyclic olefins. The results are provided inTable 13.

TABLE 13 Ring insertion cross metathesis of SBO and Cyclic OlefinsCyclic Cyclic Olefin Conv. Reaction # Olefin mol % C827 (ppm) (%)JU-108-046 COE 20 50 66 JU-108-047 COE 50 50 67 JU-108-048 COE 100 10071 JU-108-049 COE 200 100 68 JU-108-056 CDDE 5 50 66 JU-108-057 CDDE 1050 64 JU-108-058 CDDE 20 50 72 JU-108-059 CDDE 50 50 63 JU-108-060 CDDE100 100 68 JU-108-061 CDDE 200 100 67 JU-108-062 DCPD 5 50 67 JU-108-063DCPD 10 50 76 JU-108-064 DCPD 20 50 72 JU-108-065 DCPD 50 50 72JU-108-066 DCPD 100 100 69 JU-108-067 DCPD 200 100 69 JU-108-050 CDTE 550 68 JU-108-051 CDTE 10 50 68 JU-108-052 CDTE 20 50 69 JU-108-053 CDTE50 50 66 JU-108-054 CDTE 100 100 73 JU-108-055 CDTE 200 100 75JU-108-090 ENB 20 50 73 JU-108-091 ENB 50 50 82 JU-108-092 ENB 100 10074 JU-108-093 ENB 200 100 78 COE, CDDE, DCPD, CDTE and ENB do not haveany inhibitory effect on the metathesis catalyst.

COE, CDDE, DCPD, CDTE and ENB do not have an inhibitory effect on themetathesis catalyst.

Example 15

Ring opening cross metathesis was carried out according to the GeneralMetathesis Procedure using RMSBO as olefinic substrate and COE, CDDE,DCPD, CDTE and ENB as cyclic olefins. The results are provided in Table14.

TABLE 14 Ring insertion cross metathesis of RMSBO and Cyclic OlefinsRatio Cyclic of 9C15 Cyclic Olefin C827 Conv. Product ester to Reaction# Olefin mol % (ppm) (%) a Solid^(a) palmitate RLP 66-084 none 0 50 68No 1.40 JU-108-044 COE 5 50 66 1.16 JU-108-045 COE 10 50 66 1.08JU-108-068 COE 20 50 77 0.59 JU-108-069 COE 50 50 73 0.51 JU-108-070 COE100 100 solid Y JU-108-071 COE 200 100 solid Y JU-108-094 CDDE 50 50 —JU-108-095 CDDE 100 100 73 0.42 JU-108-096 CDDE 200 100 73 Y 0.34JU-108-078 DCPD 5 50 76 0.81 JU-108-079 DCPD 10 50 73 0.78 JU-108-080DCPD 20 50 73 0.59 JU-108-081 DCPD 50 50 68 JU-108-082 DCPD 100 100 72JU-108-083 DCPD 200 100 solid Y JU-108-072 CDTE 5 50 71 0.66 JU-108-073CDTE 10 50 71 0.64 JU-108-074 CDTE 20 50 72 0.55 JU-108-075 CDTE 50 5069 0.49 JU-108-076 CDTE 100 100 solid Y JU-108-077 CDTE 200 100 solid YJU-108-084 ENB 5 50 79 0.74 JU-108-085 ENB 10 50 75 0.70 JU-108-086 ENB20 50 76 0.73 JU-108-087 ENB 50 50 77 0.70 JU-108-088 ENB 100 100 741.06 JU-108-089 ENB 200 100 81 1.08 ^(a)Metathesis product was a solidor precipitated.

COE, CDDE, DCPD, CDTE and ENB do not have an inhibitory effect on themetathesis catalyst. The decrease in the 9C15 ester to palmitate ratioindicates that the cyclic olefins are ring opening cross metathesizingwith SBO to form new products.

Example 16

Ring opening cross metathesis was carried out according to the GeneralMetathesis Procedure using various olefinic substrates and cyclicolefins. The results are provided in Table 15.

TABLE 15 Ring insertion cross metathesis of SBO (batch F5L19) or RMSBOwith Cyclic Olefins Seed Cyclic Cyclic Olefin C827 Conv. Reaction # OilOlefin mol % (ppm) (%) Solidified^(a) JU-108-042 SBO COE 5 50 69JU-108-043 SBO COE 10 50 69 JU-108-046 SBO COE 20 50 66 JU-108-047 SBOCOE 50 50 67 JU-108-048 SBO COE 100 100  71 JU-108-049 SBO COE 200 100 68 JU-108-056 SBO CDDE 5 50 66 JU-108-057 SBO CDDE 10 50 64 JU-108-058SBO CDDE 20 50 72 JU-108-059 SBO CDDE 50 50 63 JU-108-062 SBO DCPD 5 5067 JU-108-063 SBO DCPD 10 50 76 JU-108-064 SBO DCPD 20 50 72 JU-108-065SBO DCPD 50 50 72 JU-108-066 SBO DCPD 100 100  69 JU-108-067 SBO DCPD200 100  69 JU-108-050 SBO CDTE 5 50 68 JU-108-051 SBO CDTE 10 50 68JU-108-052 SBO CDTE 20 50 69 JU-108-053 SBO CDTE 50 50 66 JU-108-054 SBOCDTE 100 100  73 JU-108-055 SBO CDTE 200 100  75 JU-108-044 RMSBO COE 550 66 JU-108-045 RMSBO COE 10 50 66 JU-108-068 RMSBO COE 20 50 77JU-108-069 RMSBO COE 50 50 73 JU-108-070 RMSBO COE 100 100  — Yes^(b)JU-108-071 RMSBO COE 200 100  — Yes^(b) JU-108-072 RMSBO CDTE 5 50 71JU-108-073 RMSBO CDTE 10 50 71 JU-108-074 RMSBO CDTE 20 50 72 JU-108-075RMSBO CDTE 50 50 69 JU-108-076 RMSBO CDTE 100 100  — Yes^(b) JU-108-077RMSBO CDTE 200 100  — Yes^(b) JU-108-078 RMSBO DCPD 5 50 76 JU-108-079RMSBO DCPD 10 50 73 JU-108-080 RMSBO DCPD 20 50 73 JU-108-081 RMSBO DCPD50 50 68 JU-108-082 RMSBO DCPD 100 100  72 No^(c) JU-108-083 RMSBO DCPD200 100  — Yes^(c) CWL-81- MO COD 100  50^(d) 29 100 monoxide JP-105.086SBO COD 100 450  10 monoxide ^(a)Metathesis product was a solid orprecipitated. ^(b)Clear jelly. ^(c)White, opaque. ^(d)Catalyst 627 used

COE, CDDE, DCPD, and CDTE do not have an inhibitory effect on themetathesis catalyst. COD monoxide has an inhibitory effect on metathesiscatalysts 827 and 627.

Example 17

Ring insertion cross metathesis was carried out according to the GeneralMetathesis Procedure using various seed oils and COE as cyclic olefin.The results are provided in Table 16.

TABLE 16 Ring insertion cross metathesis of Seed Oils with COE CyclicOlefin C827 Conv. at 2 hr Conv. at Lot # Seed Oil mol % (ppm) (%) 17 hr(%) Solidified^(a) JP.125.146 Canola 80 730 70 68 JP.125.147 Corn 79 74075 75 JP.125.148 Peanut 80 740 63 65 JP.125.149 Safflower 80 740 84 83JP.125.150 Olive 80 740 60 61 JP.125.151 Jojoba 55 510 75 Y JP.125.152Meadowfoam 85 790 79 79 Y ^(a)Metathesis product was a solid orprecipitated.

All of the seed oils in Table 16 and COE are substrates for ROCMreactions.

Example 18

Ring insertion cross metathesis was carried out according to the GeneralMetathesis Procedure using SBO/F6C13 as olefinic substrate, COE (100 mol%) as cyclic olefin, and various metathesis catalysts. The results areprovided in Table 17.

TABLE 17 Ring insertion cross metathesis of SBO and Cyclooctene^(a) withvarious catalysts Catalyst Metathesis Loading Conv. at 2 hr Conv. at 18hr Entry Lot # Catalyst (ppm) (%) (%) 1 JP.125.136 823 1000 N/D 51 2JP.125.137 601 1000 N/D 38 3 JP.125.138 801 1000 N/D 40 4 JP.125.139 8381000 N/D 15 5 JP.125.140 701 1000 N/D 36 6 JP.125.141 848 500 68 72 7JP.125.142 627 500 75 74 8 JP.125.143 697 500 27 29 9 JP.125.144 933 50072 73 10 JP.125.145 712 500 74 74 ^(a)1 mol of COE per 1 mol of SBO.

This data shows that a wide variety of metathesis catalysts willmetathesize seed oil ROCM reactions.

Example 19

Ring insertion cross metathesis was carried out according to the GeneralMetathesis Procedure using a chain transfer agent with a seed oil and acyclic olefin using 827 metathesis catalyst. The results are provided inTable 18.

The goals of these experiments were to develop reaction conditions thatyielded cyclic olefin inserted products that were terminated by thechain transfer agent. Percent Conversion (% Convers.) is defined as thepercent of substrate that has been converted to another metathesisproduct (ie 66% conversion represents new metathesis products with 34%unreacted substrate).

TABLE 18 ROCM reactions with a chain transfer agent. Chain Cyclictransfer Phase at Reaction # Substrate^(a) Olefin^(a) agent^(a) 827(ppm) 25° C. % Conv. JP.140.057A SBO (1) COE (3) 9C18DE (3) 2100 liquid— JP.140.057B SBO (1) COE (6) 9C18DE (3) 2700 liquid JP.140.057C SBO (1)COE (9) 9C18DE (3) 3300 liquid JP.140.057D SBO (1) COE (15) 9C18DE (3)3900 solid JP.140.057E SBO (1) COE (20) 9C18DE (3) 5500 solidJP.140.061A 9C18DE (1) COE (2) VNB (2) 1000 liquid JP.140.061B 9C18DE(1) COE (4) VNB (2) 1400 liquid JP.140.061C 9C18DE (1) COE (6) VNB (2)1800 solid JP.140.061D 9C18DE (1) COE (8) VNB (2) 2200 solid JP.140.061E9C18DE (1) COE (10) VNB (2) 2600 solid JP.140.067A Biodiesel (1) COE (1)BisTMS (1) 1200 liquid 66 JP.140.067B Biodiesel (1) COE (2) BisTMS (1)1500 liquid 36 JP.140.067C Biodiesel (1) COE (3) BisTMS (1) 1800 liquid39 JP.140.067D Biodiesel (1) COE (5) BisTMS (1) 2400 liquid 47JP.140.067E Biodiesel (1) COE (10) BisTMS (1) 3900 liquid 40JP.140.069A1 SBO (1)^(b) COE (4.5) BisTMS (3)^(b) 3600 liquid —JP.140.069A2 SBO (1)^(b) COE (9) BisTMS (3)^(b) 4950 liquid JP.140.069A3SBO (1)^(b) COE (13.5) BisTMS (3)^(b) 6300 liquid JP.140.069A4 SBO(1)^(b) COE (22.5) BisTMS (3)^(b) 9000 liquid JP.140.069A5 SBO (1)^(b)COE (45) BisTMS (3)^(b) 15750 liquid JP.140.069B1 SBO (1) COE (4.5)BisTMS (3) 3600 liquid JP.140.069B2 SBO (1) COE (9) BisTMS (3) 4950liquid JP.140.069B3 SBO (1) COE (13.5) BisTMS (3) 6300 solid/liquidJP.140.069B4 SBO (1) COE (22.5) BisTMS (3) 9000 solid JP.140.069B5 SBO(1) COE (45) BisTMS (3) 15750 solid JP.140.070A SBO (1) COD (2.25)BisTMS (4.5) 2025 liquid JP.140.070B SBO (1) COD (4.5) BisTMS (4.5) 2625liquid JP.140.070C SBO (1) COD (6.75) BisTMS (4.5) 4725 liquidJP.140.070D SBO (1) COD BisTMS (4.5) 6375 liquid (11.25) JP.140.070E SBO(1) COD (22.5) BisTMS (4.5) 9450 liquid JP.140.071A Biodiesel (1) COD(0.5) BisTMS (1) 1050 liquid JP.140.071B Biodiesel (1) COD (1) BisTMS(1) 1200 liquid JP.140.071C Biodiesel (1) COD (1.5) BisTMS (1) 1350liquid JP.140.071D Biodiesel (1) COD (2.5) BisTMS (1) 1650 liquidJP.140.071E Biodiesel (1) COD (5) BisTMS (1) 2400 liquid JP.140.073Biodiesel (1) — BisTMS (1) 900 N/A 55 JP.140.076A1 Biodiesel (1) COE (1)BisTMS (1) 1200 liquid 95 JP.140.076A2 Biodiesel (1) COE (2) BisTMS (1)1500 liquid 96 JP.140.076A3 Biodiesel (1) COE (3) BisTMS (1) 1800 liquid97 JP.140.076A4 Biodiesel (1) COE (5) BisTMS (1) 2400 liquid/solid 98JP.140.076A5 Biodiesel (1) COE (10) BisTMS (1) 3900 solid 99JP.140.076B1 Biodiesel (1) COD (0.5) BisTMS (1) 1050 liquid 95JP.140.076B2 Biodiesel (1) COD (1) BisTMS (1) 1200 liquid 95JP.140.076B3 Biodiesel (1) COD (1.5) BisTMS (1) 1350 liquid 95JP.140.076B4 Biodiesel (1) COD (2.5) BisTMS (1) 1650 liquid 96JP.140.076B5 Biodiesel (1) COD (5) BisTMS (1) 2400 liquid 98 JP.140.082Biodiesel (1) — BisTMS (1) 900 liquid 88 ^(a)mole equivalents^(b)reacted chain transfer agent with substrate, then added cyclicolefin

ROCM was accomplished using cyclic olefins with a chain transfer agentto produce novel metathesis products as determined by GC analysis andsome of the products being solids.

Example 20

General procedure for the cross-metatheses of olefinic substrate and1-butene: Terminal olefins were synthesized by the cross metathesis1-butene and seed oils with a ruthenium metathesis catalyst. Seed oilsinclude triacylglycerides, as in soybean oil, fatty acid esters, as injojoba oil and FAMES, such as methyl esters of soybean oil (soy FAME).

1-Butene used was added to a Fisher-Porter bottle equipped with a stirbar and charged with the olefinic substrates. A solution of olefinmetathesis catalyst of an appropriate concentration was prepared inanhydrous dichloromethane (obtained from Aldrich and degassed withArgon) and the desired volume of this solution added to the olefinicsubstrate. The head of the Fisher-Porter bottle was equipped with apressure gauge and a dip-tube was adapted on the bottle. The system wassealed and taken out of the glove, box to a gas line. The vessel wasthen purged 3 times with 1-propene, pressurized to the indicatedpressure (about 50 to about 150 psi for 1-propene) and placed in an oilbath at the indicated temperature. The reaction was monitored by GCanalysis. The vial was sealed with a Teflon-seal cap and the olefinicsubstrate/alpha-olefin mixture was brought to the indicated temperature,so that the reactions are conducted under a slightly positive pressure(from 1.1 to about 2 atm, i.e. from 16 psi to about 30 psi). A solutionof olefin metathesis catalyst of an appropriate concentration wasprepared in anhydrous dichloromethane (obtained from Aldrich anddegassed with Ar) and the desired volume of this solution added to theolefinic substrate/alpha-olefin mixture via syringe through theTeflon-seal while stirring. The reaction mixture was kept at the desiredtemperature for the indicated period of time before adding a 1.0 Msolution of THMP (1 mL) via syringe through the Teflon-seal cap. Themixture was then heated at 60° C. for 1 hour, diluted with 5 mL ofdistilled water and 5 mL of hexanes and the organic phase was separatedand analyzed by GC. If the olefinic substrate is a glyceride, it istransesterified to the methyl ester prior to GC analysis.

Propenolyzed Soybean oil (PSBO): To the metathesis catalyst removedproduct from above was added to a vacuum distillation setup. The pot washeated to 150° C. under high vacuum to remove volatiles. The pot wascooled to room temp and the propenoylzed SBO was used without furtherpurification.

Ring insertion cross metathesis was carried out according to the GeneralMetathesis Procedure using PSBO, a cyclic olefin and a chain using 827metathesis catalyst loading. The results are provided in Table 19.

TABLE 19 ROCM reactions with PSBO, a cyclic olefin and a chain transferagent. Chain Phase at Cyclic Transfer 25° C. after Reaction # Seed OilOlefin Agent 827 (ppm) Work up % Conv JP.140.085A PSBO (1) — BisTBS (2)1500 liquid 71 JP.140.085B PSBO (1) — BisTBS (10) 3900 liquid/ppt 90JP.140.085C PSBO (1) COE (2) BisTBS (2) 2100 liquid 85 JP.140.085D PSBO(1) COD (1) BisTBS (2) 2100 liquid 85 JP.140.085E PSBO (1) COD (2)BisTBS (2) 2100 liquid/ppt 93 JP.140.085F PSBO (1) COE (4) — 2100 veryvisc 71 JP.140.085G PSBO (1) COD (2) — 2100 very visc 89 JP.140.085HPSBO (1) COD (4) — 2100 solid 81 JP.140.086A A — — liquid 71 JP.140.086CB — — — liquid 85 JP.140.086D C — — — liquid 85 JP.140.087^(a) PSBO (1)COE (4) — 2100 liquid 73 JP.140.088^(b) PSBO (1) — BisTBS (10) 3900liquid 94 JP.140.090 PSBO (1) COE (2) BisTBS (2) 2100 ND 96 JP.140.091PSBO (1) COE (2) BisTBS (2) 2100 ND 94 JP.140.089 9DA (1) COE (2) BisTBS(1) 1200 ND — JP.140.092 9DA (1) COD (2) BisTBS (1) 1500 ND —JP.140.098A PSBO (1) COE (2) — 100 ND 74 JP.140.098B PSBO (1) COE (2) —200 ND 74 JP.140.098C PSBO (1) COE (2) — 400 ND 74 JP.140.098D PSBO (1)COD (2) — 140 ND 83 JP.140.098E PSBO (1) COD (2) — 280 ND 83 JP.140.098FPSBO (1) COD (2) — 560 ND 83 JP.140.099 PSBO (1) COD (2) — 2100 ND 83JP.140.100 PSBO (1) COE (2) — 1500 ND 75 JP.140.105A PSBO (1) COE (2) —50 ND 68 JP.140.105B PSBO (1) COE (2) — 125 ND 70 JP.140.105C PSBO (1)COE (2) — 150 ND 69 JP.140.105D PSBO (1) COD (2) — 70 ND 79 JP.140.105EPSBO (1) COD (2) — 175 ND 79 JP.140.105F PSBO (1) COD (2) — 210 ND 83 A= Deprotected product from JP.140.085A which was reanalyzed B =Deprotected product from JP.140.085C which was reanalyzed C =Deprotected product from JP.140.085D which was reanalyzed ^(a)Scale Upof JP.140.085F ^(b)Repeated JP.140.085B

Propenolyzed soybean oil is a good substrate for ROCM reactions withcyclic olefins and a chain transfer agent. Good to high conversions wereobtained in the reactions.

Example 21

Table 20 Contains GPC data for numerous ROCM reactions. The goal of thisstudy was to understand the reaction conditions that would produce thedesired ROCM products.

TABLE 20 GPC Data for ROCM Reactions using 827 metathesis catalysts.Equiv of Cyclic Olefins to Mn Mw MP PDI* Cyclic Substrate 827 Conv(Major Peak vs. PSS Notebook # Substrate Olefin (mol/mol) (ppm) (%)reported in Daltons) JP.140.009D 9C18 COE 5 1000 85 2845 3645 3294 1.28JP.140.024A 9C18 COE 10 1800 90 4072 6441 7368 1.58 JP.140.024C 9C18 COE20 3500 96 8578 15840 15518 1.85 JP.140.010E 9C18DE COE 10 1800 90 29244487 3923 1.53 JP.140.025B 9C18DE COE 15 2700 94 5685 8504 8712 1.5JP.140.025C 9C18DE COE 20 3500 96 7165 11265 11511 1.57 JP.140.027A MOCOE 10 1800 84 3713 5922 6953 1.6 JP.140.027B MO COE 15 2700 95 61879219 9292 1.49 JP.140.027C MO COE 20 3500 96 6005 10416 11470 1.73JP.140.028A CF COE 10 1800 80 4298 6258 6656 1.46 JP.140.028B CF COE 152700 87 6029 9057 9241 1.5 JP.140.028C CF COE 20 3500 90 7650 1167712157 1.53 JP.140.021F Castor Oil COE 20 2000 84 5643 11222 21449 1.99JP.140.033A1 9C18 COE 5 1000 99 2581 3137 2786 1.22 JP.140.033A2 9C18COE 10 1800 98 3295 4964 5513 1.51 JP.140.033A3 9C18 COE 20 3500 99 54269130 9954 1.68 JP.140.033B1 9C18DE COE 10 1800 NYD 2735 4084 3796 1.49JP.140.033B2 9C18DE COE 15 2700 NYD 3738 5896 6710 1.58 JP.140.033B39C18DE COE 20 3500 NYD 4630 7651 8454 1.65 JP.140.033C1 MO COE 10 180099 2949 4263 4125 1.45 JP.140.033C2 MO COE 15 2700 99 3970 6377 69211.61 JP.140.033C3 MO COE 20 3500 99 5025 9242 9495 1.84 JP.140.039ACastor — — — — 40 68 64 1.68 FAME JP.140.012A CF COE 0.5 1000 42 38 7977 2.07 JP.125.206A CF COE 1 1000 48 1239 1293 1059 1.05 JP.140.012B CFCOE 2 1000 69 1711 1859 1322 1.09 JP.140.012C CF COE 3 1000 75 1879 21471758 1.14 JP.140.012D CF COE 5 1000 84 2021 2537 2367 1.25 JP.140.033D1CF COE 10 1800 99 3089 4804 5601 1.55 JP.140.033D2 CF COE 15 2700 994050 6720 7267 1.66 JP.140.033D3 CF COE 20 3500 99 5852 9607 10030 1.64JP.140.039B Castor Oil — — — — 1442 1459 1486 1.01 JP.140.036A CastorOil — — 600 ND 11896 17024 31181 1.43 JP.140.036B Castor Oil COE 3 1200ND 5345 8439 11887 1.58 JP.140.036C Castor Oil COE 9 2400 ND 3980 770713390 1.94 JP.140.036D Castor Oil COE 15 3600 ND 5141 8773 14238 1.71JP.140.044 Castor Oil COE 20 4600 ND 8235 24287 54459 2.95 JP.140.033ECastor Oil COE 20 2000 ND 5563 18050 38940 3.24 JP.140.036E Castor OilCOE 30 6600 ND 8237 17364 32816 2.11 JP.140.039C — COE — — — 75 90 941.19 JP.140.003 — COE — 1000 — 4910 9626 7393 1.96 JP.140.039D C12 — — —— 65 JP.140.037A MO COD 1 600 91 44 397 86 8.98 JP.140.037B MO COD 51100 98 1187 2044 2196 1.72 JP.140.037C MO COD 10 2100 99 2752 3751 37251.36 JP.140.037D CF COD 1 600 66 523 719 286 1.37 JP.140.037E CF COD 51100 90 1849 2288 2201 1.25 JP.140.037F CF COD 10 2100 95 2642 3705 40101.4 JP.140.038A MO PBD 1 600 92 72 189 45 2.6 JP.140.038B MO PBD 5 110091 212 754 488 3.56 JP.140.038C MO PBD 10 2100 97 600 1350 1327 2.25JP.140.038D CF PBD 1 600 54 28 187 29 6.59 JP.140.038E CF PBD 5 1100 76541 945 568 1.75 JP.140.038F CF PBD 10 2100 92 582 1322 1368 2.27JP.140.041A1 Castor Oil COD 3 1800 ND 4262 7773 12212 1.82 JP.140.041B1Castor Oil COD 9 4200 ND 6309 11466 18572 1.82 JP.140.041C1 Castor OilCOD 15 6600 ND 4479 10619 20058 2.37 JP.140.041D1 Castor Oil COD 20 8600ND 4022 10055 20165 2.5 JP.140.041E1 Castor Oil COD 30 12600 ND 628612014 21854 1.91 JP.140.041A2 Castor Oil PBD 3 1200 ND 3619 8122 76412.24 JP.140.041B2 Castor Oil PBD 9 2400 ND 5134 11159 9756 2.17JP.140.041C2 Castor Oil PBD 15 3600 ND 5695 11684 10560 2.05JP.140.041D2 Castor Oil PBD 20 4600 ND 2200 7417 8214 3.37 JP.140.041E2Castor Oil PBD 30 6600 ND 2108 6933 7776 3.29 JP.140.043A 9C18 — — ND338 340 338 1 JP.140.043B 9C18DE — — ND 421 424 425 1.01 JP.140.043C MO— — ND 382 387 381 1.01 JP.140.043D MO — 200 ND 381 386 383 1.01JP.140.043E — PBD — — ND 4938 8145 7320 1.65 JP.140.043F — PBD — 200 ND3379 8523 8020 2.52 JP.140.043G — COD — — ND 490 493 500 1.01JP.140.043H — COD — 400 ND 34375 45119 53596 1.31 JP.140.043I SBO — — ND1260 1270 1283 1.01 JP.140.043J SBO — 900 ND 7711 10422 6108 1.35JP.140.045 CF — — 200 ND 528 537 540 1.02 JP.140.042 Castor Oil COD 3012600 ND 9769 30449 73647 3.12

The data demonstrate that numerous acyclic olefins can be run under ROCMreaction conditions to produce the desired high molecular weightproducts. Many of the products have good PDIs ranging from 1 to 2, whichrepresent products that are useful in industrial applications.

1. A method for carrying out a catalytic ring-opening cross-metathesisreaction, comprising contacting (a) at least one olefinic substrate,wherein the olefinic substrate comprises an esterification product of anunsaturated fatty acid with an alcohol, with (b) at least one cyclicolefin as a cross metathesis partner, in the presence of (c) a rutheniumalkylidene olefin metathesis catalyst, (d) under conditions effective toallow ring insertion cross metathesis whereby the cyclic olefin issimultaneously opened and inserted into the olefinic substrate.
 2. Themethod of claim 1, wherein the alcohol is a saturated alcohol.
 3. Themethod of claim 2, wherein the saturated alcohol is monohydric.
 4. Themethod of claim 2, wherein the saturated alcohol is dihydric orpolyhydric.
 5. The method of claim 4, wherein the saturated alcohol isselected from 1,2 dihydroxypropane and glycerol.
 6. The method of claim1, wherein the at least one olefinic substrate comprises amonoglyceride, a diglyceride, a triglyceride, or a mixture thereof. 7.The method of claim 1, wherein the unsaturated fatty acid comprises aseed oil.
 8. The method of claim 6, wherein the olefinic substrate hasthe structure of formula (I)

wherein R^(V), R^(VI), and R^(VII) are independently selected fromhydrogen, C₁ to C₃₆ hydrocarbyl, C₁ to C₃₆ substituted hydrocarbyl, C₁to C₃₆ heteroatom-containing hydrocarbyl, C₁ to C₃₆ substitutedheteroatom-containing hydrocarbyl, and functional groups, provided thatat least one of R^(V), R^(VI), and R^(VII) is other than hydrogen andcomprises an internal olefin.
 9. The method of claim 8, wherein R^(V),R^(VI), and R^(VII) are independently selected from C₁ to C₁₅ alkylene.10. The method of claim 9, wherein R^(V), R^(VI), and R^(VII) areindependently selected from C₄ to C₁₂ alkylene.
 11. The method of claim8, wherein each of R^(V), R^(VI), and R^(VII) is C₁ to C₃₆ hydrocarbylcontaining zero to two double bonds and optionally substituted with oneor two hydroxyl groups.
 12. The method of claim 11, wherein each ofR^(V), R^(VI), and R^(VII) is C₁ to C₁₈ hydrocarbyl containing zero totwo double bonds and optionally substituted with one or two hydroxylgroups.
 13. The method of claim 1, wherein the cyclic olefin is anoptionally substituted, optionally heteroatom-containing,mono-unsaturated, di-unsaturated, or poly-unsaturated C₅ to C₂₄hydrocarbon.
 14. The method of claim 13, wherein the cyclic olefin is amono-unsaturated, diunsaturated, or poly-unsaturated C₆ to C₁₆hydrocarbon optionally substituted with one or two hydroxyl groups andoptionally containing an ester linkage.
 15. The method of claim 14,wherein the cyclic olefin is mono-unsaturated, diunsaturated, ortri-unsaturated.
 16. The method of claim 15, wherein the cyclic olefinis mono-unsaturated.
 17. The method of claim 1, wherein the at least onecyclic olefin is a mixture of a cyclic olefinic hydrocarbon and a cyclicalkenol.
 18. The method of claim 1, wherein the molar ratio of theolefinic substrate to the cyclic olefin is in the range of about 1:2 toabout 1:10000.
 19. The method of claim 18, wherein the molar ratio ofthe olefinic substrate to the cyclic olefin is in the range of about 1:5to about 1:1000.
 20. A method for carrying out a catalytic ring-openingcross-metathesis reaction, comprising contacting (a) at least oneolefinic substrate, wherein the olefinic substrate comprises at leastone unsaturated moiety, with (b) at least one cyclic olefin as a crossmetathesis partner, in the presence of (c) a ruthenium alkylidene olefinmetathesis catalyst, (d) under conditions effective to allow ringinsertion cross metathesis whereby the cyclic olefin is simultaneouslyopened and inserted into the olefinic substrate, wherein the at leastone cyclic olefin is a mixture of a cyclic olefinic hydrocarbon and acyclic alkenol, and wherein the olefinic substrate, the cyclic olefinichydrocarbon, and the cyclic alkenol are in a ratio of approximately1:50:50.
 21. A method for carrying out a catalytic ring-openingcross-metathesis reaction, comprising contacting (a) at least oneolefinic substrate, wherein the olefinic substrate comprises at leastone unsaturated moiety, with (b) at least one cyclic olefin as a crossmetathesis partner, in the presence of (c) a ruthenium alkylidene olefinmetathesis catalyst, (d) under conditions effective to allow ringinsertion cross metathesis whereby the cyclic olefin is simultaneouslyopened and inserted into the olefinic substrate, wherein the at leastone cyclic olefin is a mixture of a cyclic olefinic hydrocarbon and acyclic alkenol, and wherein the molar ratio of the cyclic olefinichydrocarbon to the cyclic alkenol is in the range of about 1:1 to about1:100.
 22. The method of claim 21, wherein the molar ratio of the cyclicolefinic hydrocarbon to the cyclic alkenol is in the range of about 1:1to about 1:10.
 23. A method for carrying out a catalytic ring-openingcross-metathesis reaction, comprising contacting (a) at least oneolefinic substrate, wherein the olefinic substrate comprises at leastone unsaturated moiety, with (b) at least one cyclic olefin as a crossmetathesis partner, in the presence of (c) a ruthenium alkylidene olefinmetathesis catalyst, (d) under conditions effective to allow ringinsertion cross metathesis whereby the cyclic olefin is simultaneouslyopened and inserted into the olefinic substrate, wherein the at leastone cyclic olefin is a mixture of a cyclic olefinic hydrocarbon and acyclic alkenol, and wherein the molar ratio of the cyclic olefinichydrocarbon to the cyclic alkenol is in the range of about 100:1 toabout 1:1.
 24. The method of claim 23, wherein the molar ratio of thecyclic olefinic hydrocarbon to the cyclic alkenol is in the range ofabout 10:1 to about 1:1.
 25. The method of claim 1, wherein thecontacting is carried out in an inert atmosphere.
 26. A method forcarrying out a catalytic ring-opening cross-metathesis reaction,comprising contacting (a) at least one olefinic substrate, wherein theolefinic substrate comprises at least one unsaturated moiety, with (b)at least one cyclic olefin as a cross metathesis partner, in thepresence of (c) a ruthenium alkylidene olefin metathesis catalyst, (d)under conditions effective to allow ring insertion cross metathesiswhereby the cyclic olefin is simultaneously opened and inserted into theolefinic substrate, wherein the contacting is carried out in anoxygen-containing atmosphere.
 27. The method of claim 1, wherein thecatalyst is present in an amount that is less than about 1000 ppmrelative to the olefinic substrate.
 28. The method of claim 27, whereinthe catalyst is present in an amount ranging from about 50 ppm to about300 ppm relative to the olefinic substrate.
 29. The method of claim 1,wherein the ruthenium alkylidene olefin metathesis catalyst has thestructure of formula (II)

wherein: M is ruthenium; n is 0 or 1; m is 0, 1, or 2; L¹, L² and L³ areneutral electron donor ligands; X¹ and X² are anionic ligands; and R¹and R² are independently selected from hydrogen, hydrocarbyl,substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substitutedheteroatom-containing hydrocarbyl, and functional groups; wherein anytwo or more of X¹, X², L¹, L², L³, R¹, and R² can be taken together toform a cyclic group, and further wherein anyone of X¹, X², L¹, L², L³,R¹, and R² can be attached to a support.
 30. The method of claim 29,wherein: n and m are 0; R¹ is hydrogen, and R² is selected from C₁-C₂₀alkyl, C₂-C₂₀ alkenyl, and C₅-C₂₀ aryl, optionally substituted with oneor more moieties selected from C₁-C₆ alkyl, C₁-C₆ alkoxy, and phenyl; L¹and L² are independently selected from phosphine, sulfonated phosphine,phosphite, phosphinite, phosphonite, arsine, stibine, ether, amine,amide, imine, sulfoxide, carboxyl, nitrosyl, pyridine, substitutedpyridine, imidazole, substituted imidazole, pyrazine, and thioether; andX¹ and X² are independently selected from hydrogen, halide, C₁-C₂₀alkyl, C₅-C₂₀ aryl, C₁-C₂₀ alkoxy, C₅-C₂₀ aryloxy, C₂-C₂₀alkoxycarbonyl, C₆-C₂₀ aryloxycarbonyl, C₂-C₂₀ acyl, C₂-C₂₀ acyloxy,C₁-C₂₀ alkylsulfonato, C₅-C₂₀ arylsulfonato, C₁-C₂₀ alkylsulfanyl,C₅-C₂₀ arylsulfanyl, C₁-C₂₀ alkylsulfinyl, or C₅-C₂₀ arylsulfinyl, anyof which, with the exception of hydrogen and halide, are optionallyfurther substituted with one or more groups selected from halide, C₁-C₆alkyl, C₁-C₆ alkoxy, and phenyl.
 31. The method of claim 29, wherein L¹has the structure of formula (III)

in which: X and Y are heteroatoms selected from N, O, S, and P; p iszero when X is O or S, and p is 1 when X is N or P; q is zero when Y isO or S, and q is 1 when Y is N or P; Q¹, Q², Q³, and Q⁴ areindependently selected from hydrocarbylene, substituted hydrocarbylene,heteroatom-containing hydrocarbylene, substituted heteroatom-containinghydrocarbylene, and —(CO)—, and further wherein two or more substituentson adjacent atoms within Q may be linked to form an additional cyclicgroup; w, x, y, and z are independently zero or 1; and R³, R^(3A), R⁴,and R^(4A) are independently selected from hydrogen, hydrocarbyl,substituted hydrocarbyl, heteroatom-containing hydrocarbyl, andsubstituted heteroatom-containing hydrocarbyl, such that the transitionmetal complex is a ruthenium carbene complex having the structure offormula (IV)

wherein any two or more X¹, X², L², L³, R¹, R², R³, R^(3A), R⁴ andR^(4A) can be taken together to form a cyclic group, and further whereinanyone or more of X¹, X², L², L³, R¹, R², R³, R^(3A), R⁴ and R^(4A) maybe attached to a support.
 32. The method of claim 31, wherein m, w, x,y, and z are zero, X and Y are N, and R^(3A) and R^(4A) are linked toform -Q-, such that the ruthenium carbene complex has the structure offormula (VI)

wherein Q is a hydrocarbylene, substituted hydrocarbylene,heteroatom-containing hydrocarbylene, or substitutedheteroatom-containing hydrocarbylene linker, and further wherein two ormore substituents on adjacent atoms within Q may be linked to form anadditional cyclic group.
 33. The method of claim 32, wherein Q has thestructure —CR¹¹R¹²—CR¹³R¹⁴— or —CR¹¹═CR¹³—, wherein R¹¹, R¹², R¹³, andR¹⁴ are independently selected from hydrogen, hydrocarbyl, substitutedhydrocarbyl, heteroatom-containing hydrocarbyl, substitutedheteroatom-containing hydrocarbyl, and functional groups, and or whereinany two of R¹¹, R¹², R¹³, and R¹⁴ may be linked together to form asubstituted or unsubstituted, saturated or unsaturated ring.
 34. Themethod of claim 33, wherein: R¹ is hydrogen, and R² is selected fromC₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, and aryl, optionally substituted with oneor more moieties selected from C₁-C₆ alkyl, C₁-C₆ alkoxy, and phenyl; L²is selected from phosphine, sulfonated phosphine, phosphite,phosphinite, phosphonite, arsine, stibine, ether, amine, amide, imine,sulfoxide, carboxyl, nitrosyl, pyridine, substituted pyridine,imidazole, substituted imidazole, pyrazine, and thioether; X¹ and X² areindependently selected from hydrogen, halide, C₁-C₂₀ alkyl, C₅-C₂₀ aryl,C₁-C₂₀ alkoxy, C₅-C₂₀ aryloxy, C₂-C₂₀ alkoxycarbonyl C₆-C₂₀aryloxycarbonyl, C₂-C₂₀ acyl, C₂-C₂₀ acyloxy, C₁-C₂₀ alkylsulfonato,C₅-C₂₀ arylsulfonato, C₁-C₂₀ alkylsulfanyl, C₅-C₂₀ arylsulfanyl, C₁-C₂₀alkylsulfinyl, or C₅-C₂₀ arylsulfinyl, any of which, with the exceptionof hydrogen and halide, are optionally further substituted with one ormore groups selected from halide, C₁-C₆ alkyl, C₁-C₆ alkoxy, and phenyl;R³ and R⁴ are aromatic, substituted aromatic, heteroaromatic,substituted heteroaromatic, alicyclic, substituted alicyclic,heteroatom-containing alicyclic, or substituted heteroatom containingalicyclic, composed of from one to about five rings; and R¹² and R¹⁴ arehydrogen, and R¹¹ and R¹³ are selected from hydrogen, lower alkyl andphenyl, or are linked to form a cyclic group.
 35. The method of claim 1,wherein the catalyst is a Grubbs-Hoveyda complex.
 36. The method ofclaim 35, wherein the complex has an N-heterocyclic carbene ligandassociated with the ruthenium center.
 37. The method of claim 1, whereinthe cyclic olefin is functionalized.